The motivation of the present work was to obtain improved TiO2 photoelectrode by admixing CeO2 through sol gel process. The surface morphology, structural and PEC characterization of the TiO2 overland with CeO2 admixtures have been investigated in relation to hydrogen production through semiconductor septum photo-electro-chemical (SC-SEP PEC) solar cell. UV Vis absorption spectra show a clear enhancement in the absorption range caused by admixing CeO2. The CeO2 admixed ns TiO2 exhibited a high photocurrent and photovoltage of 14.6 mA cm(-2) and 920 mV. The ns TiO2 CeO2 electrode showed high hydrogen gas evolution rate of 13.8 1 h(-1) m(-2) in comparison to bare ns- TiO2 photoelectrode which showed 8.6 1 h(-1) m(-2) hydrogen gas evolution rates. (C) 2015 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.