The photocatalytic reductive capability of a natural semiconducting mineral, sphalerite has been studied for the first time. The sphalerite from the Huangshaping deposit of Hunan Province performed great photoreductive capability that 91.95% of the Cr6+ was reduced under 9 h visible light irradiation, higher than the 70.58% under 9.5 h UV light irradiation. The highly reductive ability results from its super negative potential of electrons in the conduction band. Furthermore, Fe substitution for Zn introduces donor states, and the oxidation process of Fe2+ to Fe3+ makes it an effective hole-scavenger. Cd and Cu substitute for Zn also reduce the bandgap and help broaden the absorbing edge towards the visible light. These substituting metal ions in natural sphalerite make it a hyper-active photocatalyst and very attractive for solar energy utilization.