The electrochemical properties of single-crystalline p-type 3C-SiC films on p-Si substrate were investigated as an electrode in H2SO4 aqueous solutions in dark and under white light illumination. The photoelectrochemical (PEC) measurements indicates the p-type 3C-SiC film on p-Si substrate can generate a cathodic photocurrent as a photocathode, which corresponds to hydrogen production, and generate an anodic photocurrent as a photo-anode, which corresponds to oxygen evolution. The surface chemical states of the films were investigated by XPS. In order to observe the surface chemical state changes after PEC test, the range of applied potential to the electrode was divided into three zones: -3.6 to 0 V, 0-1.5 V and 1.5-4 V vs. Ag/AgCl. After separated PEC tests in these three areas, XPS shows the surface of the SiC film in the range of -3.6 to 0 V and 0-1.5 V was stable without oxidation except the band bending occurred. But in the range of 1.5-4 V the film surface was oxidized due to anodic oxidation. Copyright (C) 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.