Electrochemical characteristics of photo-electrochemical cell (involving photo-anode made of TiO2, and Pt as cathode) were investigated during the light-on and the light-off regimes using the sunlight. Maximum photo-voltage of the open cell involving undoped TiO2 as photo-anode is 0.7 and 1.6 V without and with chemical bias (Delta pH= 14.6), respectively. Application of ceramic Cr-doped TiO2 (involving 1 wt% of Cr2O3) as photo-anode results in a substantial decrease or the cell voltage (to 0.8 V) despite the application of chemical bias.