In this study, we have fabricated network-like Au/ZnO nanowire arrays with special space structure using a simple photo-reduction method. The morphology and photoelectrochemical property of the network-like Au/ZnO nanowire arrays could be controlled by changing the reaction parameters such as the photo-reduction time and concentration of reagents. Moreover, their photoelectrochemical and supercapacitor performances have also been performed, revealing that the network-like Au/ZnO nanowire arrays possesses a much higher photocurrent density than the pure ZnO nanowire arrays. The enhanced photoelectrochemical performances could be originated from the surface plasmon resonance within Au nanostructure and the special space structure of network-like Au/ZnO nanowire arrays.