The top of silicon nanowires (SiNWs) arrays was coated with reduced graphene oxide (rGO) by the facile spin-coating method. The resulting SiNWs/rGO composite exhibits enhanced photoelectrochemical properties, with short-circuit photocurrent density more than 4 times higher than that of the pristine SiNWs and more than 600 times higher than that of planar Si/rGO composite. The trapping and recombination of photogenerated carriers at the surface state of SiNWs were reduced after the application of rGO. The results of electrochemical impedance spectroscopy measurements suggest that the reduction of trapping and recombination of photogenerated carriers as well as remarkably enhancement of photoelectrochemical properties can be attributed to the low charge transfer resistance at the SiNWs-rGO interface and rGO-electrolyte interface. The method and results shown here indicate a convenient and applicable approach to further exploitation of high activity materials for photoelectrochemical applications.