The exotic invasive species from the ballast water in the ship will bring about serious damages to ecosystem. Photocatalyst films have been widely studied for sterilization. In this study, ZnWO4 with different exposed facets was synthesized by hydrothermal method, and ZnWO4 film electrodes have been applied in ballast water treatment through the electro-assisted photocatalytic system. Then the samples were investigated by X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS), Field emission on scanning electron microcopy (FE-SEM), Transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DRS), BET specific surface area analysis, Fourier transform infrared (FT-IR) and Electro-chemical impedance spectra (EIS). ZnWO4 with an appropriate exposure of (0 1 1) facets ratio exhibited the best photocatalytic and photoelectrocatalytic activities. The microorganisms deactivated completely in 10 min by ZnWO4 films with 3 V bias. The mechanisms of (0 1 1) facets enhanced the photocatalytic and photoelectrocatalytic activities which were deduced based on the calculated result from the first principles. Simultaneously, appropriate exposed facets and applied bias could reduce the recombination of the photogenerated electron-hole pairs, and improve the photocatalytic activities of ZnWO4. (C) 2016 Elsevier B.V. All rights reserved.