Herein, we demonstrate the synthesis of a Bi2MoO6 nanorod array followed by the deposition of a BiVO4 absorber layer. This heterojunction yielded a photocurrent density of 250 μA cm(-2) at 0.8 VSCE, which is 21 times that produced by a planar Bi2MoO6 array under the same conditions. Moreover, in situ X-ray photoelectron spectroscopy clearly confirmed the improvement of the electron transport and charge separation afforded by the heterostructure, features that efficiently enhanced the photoelectrochemical properties of the array.