Abstract: Natural sphalerite as a natural cost-effective photocatalyst was characterized and its visible light photocatalytic activity was investigated in terms of substituting ions, impurity phases and surface defects. The substitutions of metal ions for Zn2+ alter the band structure and result in the visible light response. The coexistence of impurity semiconductors and nanosized particles in natural sphalerite samples help to prolong the lifetime of electron-hole pairs. The cleavage planes and fracture surfaces improve the photocatalytic activity of natural sphalerite by providing more active sites than perfect faces. Both the negative charge defects from the non-isoelectronic substitutions and surface elements with variable chemical valence suppressed the recombination of electron-hole pairs by their possible role of capturing photogenerated holes.