Nanopyramid-assembled three-dimensional (3D) hierarchical Cu2O stars on F-doped SnO2 coated glass (FTO) substrates have been successfully synthesized using a rapid and facile electrodeposition approach from aqueous solutions near room temperature. Combined X-ray photoelectron spectroscopy (XPS) and X-ray-induced Cu LMM Auger studies reveal only Cu2O on the surface of the samples. The Cu2O stars exhibit superior photocurrent performance over Cu2O nanoparticles in photoelectrochemical cell applications. In addition, the photocurrent of the Cu2O samples is due to water splitting.