The polyaniline (PANI) assembled on TiO2-V2O5 compound (TVC) was prepared by in-situ polymerization method. The TiO2-TVC and TiO2-TVC/PANI composite films at TVC/TiO2 molar ratio of 0.1 deposited on the ITO glass successfully prepared using spin coating technique. The products were characterized by using SEM, TGA, FTIR and electrochemical technique. The maximum electron storage of TiO2/PANI-TVC (2.17 wt % PANI in TVC/PANI) under UV stimulation is 3,689.3 C/mol, which is 30% higher than that of TiO2-TVC. This electron storage is equivalent to 96.3% of maximum capacity of TVC. This result suggests that optimal amount of PANI effect on higher efficiency of electron storage.