Nanostructure hybrid organic–inorganic composites have attracted considerable attention recently, both from the perspectives of fundamental research and their technological applications[1–3]. One approach for preparing these materials is via sol–gel process. In the inorganic matrix, components are formed in situ through hydrolysis and condensation of metal oxide precursors, while the organic matrix undergoes simultaneous polymerization. However, the sol–gel approach is limited by the evaluation of volatile biproducts and concomitant shrinkage when the hybrid is processed at elevated temperature[4, 5]. The sol–gel method is one of the most suitable methods to prepare the silica gel through siloxane linkages by the hydrolysis and condensation reactions. The silica hybrid materials greatly depend on the interaction between the organic polymers and inorganic alkoxides and their homogeneous distribution through hydrogen bonding, covalent bonding, formation of stereo regular complex, and π-π and ionic interactions[6–8]. The Michael addition reaction in polymer synthesis and applications in emerging technologies, composites, coatings, and optical coatings are outlined in the article. Organic–inorganic hybrid nanocomposites are a new category of high-performance materials which is currently an area that has received extensive interests for other matrix of polyimide (PI)-SiO2[10, 11], PI-Al2O3, and PI-TiO2[13–15]; these composites have been successfully synthesized. Many researches have been focusing on developing the PI-inorganic hybrid nanocomposites, such as the use of dianhydride and diamine to synthesize the PI matrix and the use of metal alkoxides to provide the inorganic network. Nanocomposites can be prepared through different processes. Among those successful ones[16–19], the in situ polymerization and gelation reaction is a type of processing in which the inorganic phase was generated from the metal alkoxide precursors through hydrolysis and condensation reactions that took place simultaneously with the polymerization reaction. Wang and Chang and other researchers[20, 21] prepared the hybrid nanocomposite films of TiO2 in the PI matrix from 2,5-bis (4-aminophenyl)3,4-oxadiazole, 4,4′-oxydiaphthalic anhydride, and titanium precursors by an in situ sol–gel process. The titanium precursor was prepared by mixing tetraethyl titanate (TET) and acetyl acetone (acac) in the solution of alcohol and water. These nanocomposites exhibited fairly good optical transparency at 40 wt.% of TiO2 content. The transmission electron microscope (TEM) results showed that the size of the TiO2 particle increased from 10 to 40 nm[20–22]. Several successful examples of in situ polymerization and gelation reaction processes could be found in the literature. The polymer nanocomposites were prepared using poly(amic acid) solution by the condensation of 3,3′,4,4′-benzonphenone tetra carboxylic dianhydride and 4,4′-oxydianhydride 4,4′-oxydianiline (ODA) then added TET followed by thermal imidization from PI/TiO2 hybrid nanocomposites. They reported that nanosized inorganic TiO2 network dispersed in PI films at an average diameter of 1.5 nm at TiO2 content of 12 wt.%[22–24]. The poly(amide-imide)/TiO2 (PAI/TiO2) nanocomposite films obtained 4,4′-oxy(phenyl trimellimide) and ODA using tert-butyl benzoic acid as the mono functional endcapper; with TET, these composite films exhibited high transparency and had well-dispersed nanosized TiO2 in the PAI matrix[25–27]. The size of the TiO2 network increased from 5 to 50 nm when the TiO2 content was increased from 4% to 18% by weight. While large sized, nanosized inorganic particles made the nanocomposite films, transparent in such the particle size effect, hydrogen bonding between the amide group in the PAI and the hydroxyl groups on the inorganic oxides played an important role in making such small particle size possible[28–30]. According to these reports, the sol–gel process is one of the most commonly used processes of preparing titanium dioxide. However, in the process for preparing titanium dioxide, there are a few technical problems that must be resolved. First of all the titanium alkoxide is a highly reactive compound when it is exposed to moisture, and white precipitate will form rapidly. In order to prepare nanosized TiO2 suspension solution, the pH values and the use of chelating agents are crucial in the reaction steps. It is reported elsewhere in the literature that[32–34] prepared high refractive index thin films of pyrometallic dianhydride titania hybrid materials from dianhydride, γ-aminopropyltriethoxy silane (γ-APS), and titanium isopropoxide via sol–gel process followed by spin coating and multi-step backing; through adjustment in the concentration and reaction time, they were able to produce thin films of hybrid inorganic content at 59.2%. Therefore, the transparent polymer hybrid used for lenses has about 90% transmittance/cm. Typical materials PMMA, PC, polystyrene, and styrene-MMA copolymers have been used for the lenses in projection television and lenses for using compact disk. The plastic materials in optical disk circuit need to be highly transparent, resistant to heat, low impurities, and must have a low double refractive index and low fluidity. However, no materials with these properties have yet been found or developed. Semiconductor-mediated photocatalytic oxidation has been accepted as a promising method for the removal of organic contaminants from waste water. Among the semiconductors employed, TiO2 is known to be a good photocatalyst because of its high photosensitivity, non-toxicity, easy availability, strong oxidizing power, and long-term stability[35, 36]. Existing bulk semiconducting materials possess low surface area, less absorption property, and fast electron–hole recombination. In order to circumvent such problems, researchers are interested in recent days in the synthesis of nanomaterials for environmental applications[34–36]. The polymer metal oxide hybrid nanocomposites contained bimetallic dopants of the titanium and barium oxides. The precursors of metal oxides were formed from tetrabutyl titanate (TBT) and barium carbonate, which were then mixed with poly(amic acid) solution followed by thermal imidization. The synthesized hybrid nanocomposites with inorganic particles are smaller than 50 nm, and the dielectric constant increased from 3.5 to 4.2 when the inorganic content increased from 1 to 10 wt.%. Polyimides are considered to be one of the most important super-engineering materials due to their thermal stability as well as the superior mechanical properties at elevated temperature[37, 38]. Since the polyimide/silica hybrid materials have been prepared successfully through the sol–gel process, more attention were given to the field[34–40]. Recently, metal-containing polyimide/titania hybrids were also prepared. The key challenge for the preparation of the hybrid materials is how to control the phase separation between the organic and inorganic moieties. The phase behavior is connected with the interaction between the organic segment and the inorganic network in the hybrids. Hydrogen bonding or covalent bonding is usually used to prevent phase separation. Recently, the sol–gel process is a novel technique for the preparation of nanocrystalline TiO2. It has been demonstrated that through the sol–gel process, the physico-chemical and electrochemical properties of TiO2 can be modified to improve its efficiency. It provides a simple and easy means of synthesizing nanoparticles at ambient temperature under atmospheric pressure, and this technique does require simple setup. Since this method is a solution process, it has all the advantages over other preparation techniques in terms of purity, homogeneity, felicity, and flexibility in introducing dopants in large concentrations, stoichiometry control, ease of processing, and composition control. Through the sol–gel process, the growth of TiO2 colloids in sub-micrometer range can be effectively controlled by hydrolysis and condensation of titanium alkoxides in aqueous medium. Nanosize TiO2 used so far in photocatalytic applications has been prepared by hydrolysis of titanium precursors followed by annealing, flame synthesis, and hydrothermal and sol–gel processes. In most studies, attempts have been made to enhance the photocatalytic activity of TiO2 only by varying the calcination temperature and, in a few cases, aging period and drying conditions[40–43]. Among the various techniques under the development, the sol–gel process has been found to be extremely suitable as it enables good control of composition and optical behavior of the final nanomaterials. In recent years, silica-titania hybrid organic–inorganic materials have been studied as a promising system for photonic applications[41–43], and low loss wave guide based on the organically modified alkoxides has been fabricated by the sol–gel process. Therefore, the sol–gel integrated optics is beginning to show potential applications, and it stimulates the studies on optical wave guide material which have been explored for a long time and such sol–gel materials used for optical applications. In the area of advanced oxidation technology, titanium dioxide semiconductor photocatalysis has been widely studied because of its potential application in air clean-up and water purification. TiO2 is largely used as photocatalyst due to its beneficial characteristics: high photocatalytic efficiency, physical and chemical stability, low cost, and low toxicity[40–42]. TiO2/SiO2 composites are very promising in the field of heterogeneous photocatalysis since they could provide simultaneously enhanced photocatalytic and thermal properties compared to pure TiO2 photocatalyst. It has been reported that photocatalytic reactivity of TiO2/SiO2 nanocomposites is highly dependent on the Ti/Si ratios. The photocatalytic activity and mechanical stability were reported to improve by the addition of about 50% SiO2[40–48]. Moreover, in the present work, an attempt has been made to develop the silica/titania-incorporated transparent maleimide-functionalized polystyrene to improve the thermochemical and optical characteristics with γ-APS, TEOS, and titanium isopropoxide through the Michael addition reaction at relatively low temperature through the sol–gel method. Furthermore, the organic–inorganic transparent hybrid nanocomposite materials were characterized by FTIR, nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), differential scanning calorimeter (DSC), optical images, scanning electron microscope (SEM), and TEM analyses.