Zinc tungstate (ZnWO4) was synthesized by hydrothermal method with the assistance of three kinds of surfactant (EG, CTAB, and SDBS). The ZnWO4 films were employed as anode to inactivate marine microorganisms through photoelectrocatalytic technology under 2 V bias voltage and 254 nm UV irradiation. Results showed that in contrast to the original sample, all the samples which synthesized with the assistance of surfactants demonstrated enhanced activity. The inactivation time of EG sample was 7 min, which was 36% shorter than that of ORI sample (11 min). SEM and TEM revealed that surfactants can influence the morphology and microstructure of ZnWO4 . Fourier transform infrared spectroscopy and cyclic voltammetry showed that the EG sample can produce more 'OH radical, which corresponded to its hydroxyl radical-generating potential. Meanwhile, UV-vis diffuse reflectance spectroscopy showed that the EG sample had wide forbidden band and high positive valence band, thereby facilitating the production of photogenerated holes (h(+)) with strong oxidation ability.