TiO 2 /ZnO and ZnO/TiO 2 nanolayer thin films were synthesized using sol–gel method. Optical analysis revealed high transmittance of the films in the visible range with almost the same bandgap energy for the both systems. XPS technique shows stoichiometric formation of TiO 2 and ZnO on the surface of TiO 2 /ZnO and ZnO/TiO 2 layers, respectively. According to AFM observations and its data analysis, the TiO 2 /ZnO films exhibited a higher surface roughness and more effective interfaces with electrolyte during redox reactions. Based on photoelectrochemical measurements, TiO 2 /ZnO nanolayer photoanode possesses a lower charge transfer resistance and higher transient time for charge carriers (e − and h + ) and hence a higher photocurrent density under visible light irradiation as compared with the ZnO/TiO 2 nanolayer system.