The photoelectrochemical conversion behavior of SnO2film electrodes deposited by spray pyrolysis has been investigated as a function of deposition parameters and the amount of additive Sb. The photocurrent increased with increasing substrate temperature up to 400 °C, and then decreased. As the concentration of the spray solution increased, the photocurrent reached a maximum value at the concentration of 0.05 M. In Sb‐doped SnO2film electrodes, the photocurrent decreased due to the reduction of mobility and depletion layer width. These results could be explained in terms of microstructure and electrical property.