The photocurrent of hydrogen generating solid-state photoelectrochemical cell utilising a polybenzimidazole proton-conducting membrane and gaseous anode reactants has been enhanced by operation at higher temperatures. With a bias of 0 V for example, photocurrent increased from 15 to 30 μA/cm2 on moving from 25 °C to 45 °C. The increase in photocurrent, which was limited by the dehydration of the cell, was shown to have contribution from improved electrode kinetics. Modification of TiO2 surface with triazole, a conjugated heterocyclic compound, led to significant increase in photocurrent up to 4 fold increase at 0 V and 25 °C. This was attributed to improved separation of photogenerated charge carriers, as confirmed by correspondingly increased carrier lifetimes from 50 ns to 90 ns for triazole-modified TiO2. Assembly of the photoelectrochemical cell by hot-pressing induced a ̴ 0.3 eV red shift in optical absorption edge of TiO2, in agreement with a shift of its valence band maximum to higher binding energy.