Novel photocatalysts, which consist of two visible light responsive semiconductors including graphite-like carbon nitride (g-C3N4) and Fe2O3, were successfully synthesized via electrodeposition followed by chemical vapor deposition. The morphology of the g-C3N4/Fe2O3 can be tuned from regular nanosheets to porous cross-linked nanostructures. Remarkably, the optimum activity of the g-C3N4/Fe2O3 is almost 70 times higher than that of individual Fe2O3 for photoelectrochemical water splitting. The enhancement of photoelectrochemical activity could be assigned to the morphology change of the photocatalysts and the effective separation and transfer of photogenerated electrons and holes originated from the intimately contacted interfaces. The g-C3N4/Fe2O3 composites could be developed as high performance photocatalysts for water splitting and other optoelectric devices. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.