The (0.8PPV+0.2DMPPV) copolymer and silica/borosilicate composites were synthesized by sol-gel process. The organic-inorganic hybrid solution was prepared by using of (0.8PPV+0.2DMPPV) copolymer precursor solution as a raw material for organic components and TEOS and TMB for glass components. Then by drying the solution in vacuum at 5$0^{circ}C$ for 7days and subsequent heat treatment in vacuum at 15$0^{circ}C$~30$0^{circ}C$ for 2h~72h with heating rate of 0.2$^{circ}C$/min and 1.8$^{circ}C$/min, the organic-inorganic composites were synthesized. Microstructural evolution of the composites was characterized by DSC, IR spectrocopy, UV/VIS spectroscopy, and TEM. Elimination of the polymer precursor and degradation of the polymer were observed by DSC and Si-O and trans C=C absorption peaks were identified by IR spectra. The polymer was found to be successfully incorporated into the glass matrix and it was confirmed by the absorption peaks from the polymer in the UV/VIS spectra and the TEM results. The absorption peak of the composites was found to shift toward short wavelength side compared to that of the pure polymer and the amount of the blue shift increased with increasing the heat treatment temperature and heat treatment time and with decreasing the heating rate.