Urea has been proposed as a source to produce hydrogen. We describe here CdSe-sensitized TiO₂ assembled with urea electrocatalyst, Ni(OH)₂, on fluorine-doped tin oxide (FTO) coated glass (FTO/TiO₂/CdSe/Ni(OH)₂) used as photoanode for simultaneous urea oxidation and water reduction using visible light irradiation. The steady-state photoresponse of the semiconductor-catalyst electrode in the photoelectrochemical system is investigated, and the CdSe quantum confinement effect on charge transfer kinetics is investigated by employing transient absorption spectroscopy. The obtained carrier dynamics reveal the reaction mechanism and indicate the change of the CdSe band position and hence driving force for charge transfer.