The effects of grain size and dopant ZnO on the photoelectrochemical conversion in TiO2 ceramic electrodes have been investigated. The photocurrent increases with increasing grain size in the undoped TiO2 ceramic electrode. In ZnO-doped TiO2 electrodes, the photocurrent decreases with increasing ZnO up to 0.4 wt% due to decrease of donor concentration, and then with further addition of ZnO, photocurrent increases according to the formation of second phase. However, the photoresponse appears at wavelength of 420nm, which is very close to the energy band gap of TiO2, regardless of grain size and amount of ZnO.