ZnWO4 powders with grain size in range 20 nm–10 µm have been synthesized by a simple combustion method and subsequent calcinations. The photocatalytic activities of powders were tested by degradation of methylene blue solution under UV light. The luminescence spectra and luminescence decay kinetics were studied and luminescence decay time dependence on average powder-grain size was obtained. The correlation between self-trapped exciton luminescence decay time and photocatalytic activity of ZnWO4 powders was shown. A model explaining the excitonic luminescence decay time correlation with photocatalytic activity was proposed.