Tungstate oxide is a new kind of anionic semiconductor material, which has been received much attention due to its good photocatalytic performance and long-term stability. To facilitate large-scale application, the natural counterpart of tungstate oxide, wolframite, was firstly used as a visible-light mineral photocatalyst in this study. Its mineralogical and photocatalytic properties were characterized and compared with two synthetic endmember minerals, FeWO4 and MnWO4. The results showed natural wolframite in the form of (Fe,Mn)WO4, had a bandgap of only 1.5 eV, far lower than that of FeWO4 (2.3 eV) and MnWO4 (2.6 eV). Under visible-light, natural wolframite exhibited remarkable photoactivity towards degradation of methylene blue (MB, 5 mg/L) and disinfection of Escherichia coli K-12 (10(7) cfu mL(-1)) under neutral pH. The MB degradation rate in the presence of both wolframite and H2O2 was as 3-fold or 14-fold as that in the controls without light or H2O2, respectively. And the disinfection rate using wolframite was at least 5 times higher than that using MnWO4 or FeWO4. Hydroxyl radical (OH center dot), as detected by electron paramagnetic resonance, was demonstrated as the major reactive oxygen species by using different scavengers in the photocatalytic reactions. The production of OH center dot was due to both photocatalytic and photo-Fenton effects. Recycling experiments were conducted to demonstrate the longterm stability and photoactivity of wolframite, in which the MB degradation rate almost kept unchanged after three experimental rounds. Our results indicated that natural wolframite could be used as a promising visiblelight driven photocatalyst applied for large-scale wastewater treatment.