Pure phase of CeFeO3 perovskite was synthesized by using a modified microwave-assisted method and was systematically studied by photo-electrochemical (PEC) investigations for water splitting reaction. Characterization studies confirm the formation of crystalline orthorhombic single phase perovskite structure with space group Pbnm and having agglomerated sponge-like morphology with nano size grains. DRS shows broad absorption in 'UV Visible region, while taut plot also inferred estimated band gap of 1.9 eV. The photo activity of their screen printed thin film was analyzed by PEC studies, which includes photocurrent, EIS spectra, MS-plot, J-V plots. On illumination, EIS analysis of CeFeO3 reveals improved charge transfer at interfaces of semiconductor/electrolyte. The photocurrent density difference of CeFeO3 was increased to 6.9 mA cm(-2) at an applied bias of 1.5 V vs (Ag/AgCl). PEC H-2 evolution shows significant cumulative hydrogen rate of 12.3 pnol cm(-2) h(-1). All these results reveal that the microwave-synthesized CeFeO3 is a potential candidate for PEC application under the visible light illumination. (C) 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.