In this work, TiO2 nanocrystalline thin films were obtained through evaporating nfilms by Electron Beam Deposition (EBD) followed by thermal treatment. The deposition speed of n thin fims was carried out at 0.15 nm/s and 1 nm/s. The results show that after annealing at 450°C for 8 h, the obtained TiO2 thin films have nanoparticle structure with grain size of 20 nm for the n thin film deposited at the rate of 1 nm/s, whereas at the a deposition rate of 0.15 nm/s, the TiO2 has a nanorod structure with the rod length of 300 - 400 nm. The influence of thermal annealing on structure of TiO2 films have been investigated and indicated that when annealed at 450°C for 8 hours, all the To films were completely oxidized to form TiO2 films with anatase phase. Whereas, at 700°C the rutile phase was formed. The band gap of TiO2 thin films decreased with annealing temperature in both doposition rate of Ti-thin films. The response of the films annealed at 450°C presented a faster rise and fall in photocurrent under UV illumination on and off interval. Nanoporous structure TiO2 shows photoelectronic property better than that of nanorod structure. The TiO2 films were used in a photo-electrochemical (PEC) cell as a working electrode and a platinum electrode as a counter electrode. The electrolyte solution contains 1 M KCI and 0.1 M Na2S.