Natural sphalerite, which represents a new class of mineral-based catalyst, was characterized and investigated for photo-reduction of an azo dye methyl orange (MO) under visible light. After 2 h of visible light irradiation, a complete decolorization of the MO solution was achieved. The degradation rate was related to the pH conditions. Spectra from FT-IR analysis indicate an initial adsorption of MO to sphalerite via its sulfonate group. Further reduction of the adsorbed MO by sphalerite under light irradiation led to the destruction of the azo structure, as indicated by the results from UV-vis, FT-IR and ESI-MS analyses. The visible light-induced photocatalytic reductive activity of natural sphalerite was mainly attributed to the distribution of foreign metal atoms in its crystal lattice, which reduces the intrinsic bandgap of sphalerite and also broadens its spectra responding range. In addition, the high,conduction band potential of natural sphalerite may also enhance the photo-reduction of MO. (C) 2009 Elsevier B.V. All rights reserved.