Herein we report a facile and economic method to prepare nanovoid Bi2WO6 2D ordered arrays employing a simple self-assembly procedure. The electrochemical properties and performance of the 2D nanoarray as a photoanode for water splitting are investigated and compared with a conventional photoanode of similar thickness. The 2D array photoanode shows a much higher photocurrent density and photon-to-H2 conversion efficiency even with a small content of the Bi2WO6 material. The enhancement is further studied and explained on the basis of the superiority of light scattering and photogenerated hole diffusion within the 2D array structure. This work provides a facile method to improve the efficiency of solar energy conversion systems by minimizing the charge-carrier diffusion length and reducing the light reflection, as well as reducing the amount of the semiconductor material (often costly and/or rare) present in the photoanode.