Charge transfer complexes (CTC) can be readily introduced into materials by cohydrolysis-copolymerisation of bis-silylated ter-thiophenes as precursors with TMOS and TEOS in the presence of TCNQ. CTC formation is shown in the visible spectrum of the xerogel by the band at 850 nm characteristic of the TCNQ·- radical anion. Vibrational spectra have shown that strong vibration of C≡N bond at 2184, 2120 and 1595 cm-1 as peaks characteristics of CTC. The CTC bands are weak and the complex is easily destroyed by washing with acetone, which removes the TCNQ. The gelification effect of the charge transfer complexes on the hybrid materials of 2,5’’- bis(trime thoxysilyl)terthiophene/TCNQ/ TMOS showed that the peak with distance of more than 11.68 Å, formed by precursors and matrices, as a lamellar structure. The birefringence of xerogel BTS3T in presence of alkoxysilane showed that the value is near the detection limit of 0.1 – 0.4 x 10-3, which is weaker than BTS3T / THF with the birefringence value of 4.5 x 10-3.