Pt nanoparticles are the most frequently used catalyst for Si photocathode. Alternative catalyst based on transition metal or metal oxide as cathode catalyst is greatly desired to replace Pt. A mesoporous alpha-Fe2O3 thin film (80 nm) was deposited on the surface of planar p-Si using a facile atmospheric pressure chemical vapor deposition (APCVD) method through pyrolysis of ferrocene. The planar Si photocathode shows a 400% enhancement in photocurrent at 1.0 V-RHE and an anodic onset potential shift of 0.5 V upon deposition of surface mesoporous alpha-Fe2O3 layer. This composite photo electrode also shows superior photoelectrochemical performance to the Pt/planar Si photoelectrode. (C) 2016 Elsevier B.V. All rights reserved.