In this article, hierarchical flower-like ZnO nanostructures with controlled morphology and dimensions have been synthesized by solution phase approach and functionalized by Au nanoparticles (AuNPs) with the combination of electrodeposition to explore novel applications. The photocatalytic activity and lithium storage capacity of these hybrid nanostructures have been investigated. It has been found that hybrid nanostructure combining the large specific surface area, stability and catalytic activity of small AuNPs, demonstrate the higher photocatalytic activity than that of pure ZnO. Furthermore, an initial discharge capacity of 1280 mA h g-1 and a reversible capacity over 392 mA h g-1 at the 50 cycles are achieved for the Au-ZnO hybrid nanostructure, which is found to be much better than that of any previously reported ZnO anodes. The improved lithium storage capacity and cycle life of the Au-ZnO electrode result from the Li activity of Au-ZnO phase. The photocatalytic and electrochemical activity of Au-ZnO hybrid nanostructures provide a new platform for energy storage, environmental remediation and photocatalysis applications.