This paper introduces a novel composite anode that uses light to enhance current generation and accelerate biofilm formation in bioelectrochemical systems. The composite anode is composed of 316L stainless steel substrate and a nanostructured alpha-Fe2O3 photocatalyst (PSS). The electrode properties, current generation, and biofilm properties of the anode are investigated. In terms of photocurrent, the optimal deposition and heat-treatment times are found to be 30 min and 2 min, respectively, which result in a maximum photocurrent of 0.6 A m(-2). The start-up time of the PSS is 1.2 days and the maximum current density is 2.8 A m(-2), twice and 25 times that of unmodified anode, respectively. The current density of the PSS remains stable during 20 days of illumination. Confocal laser scanning microscope images show that the PSS could benefit biofilm formation, while electrochemical impedance spectroscopy indicates that the PSS reduce the charge-transfer resistance of the anode. Our findings show that photo-electrochemical interaction is a promising way to enhance the biocompatibility of metal anodes for bioelectrochemical systems. (C) 2016 Elsevier B.V. All rights reserved.