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 V_SCE, 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.