Photoelectrochemical studies on TiO₂ doped with Ce₂O₃ or CeO₂ took place in aqueous solutions of [Fe(CN)₆]^4- as the source of hydrated electrons. Our studies show that doping TiO₂ with CeO₂ gave better photocatalytic reduction of [Fe(CN)₆]^3- than TiO₂ doped with Ce₂O₃. However the TiO₂ assemblies doped with either Ce(III) or Ce(IV) oxides give less photochemical reduction of [Fe(CN)₆]^3- that the oxides of pure metals (Ti or Ce). In both cases a lowering of the band gaps of TiO₂ was noticed. Immobilized TiO₂ doped with Ce oxides on a FTO (Fluorine Ten Oxide) surface gave greater photocurrent with I₂/I₃^– than that recorded for [Fe(CN)₆]^3-/4- redox systems. Our studies indicate that the TiO₂ doped with Ce₂O₃ or CeO₂ maintained photoactivity after being immobilized in thin solid sheets and can be used in all solid state photoelectron-chemical cells.