The natural semiconducting mineral rutile and sphalerite exhibited highly photocatalytic activities on degradation of methyl orange under visible light irradiation. The isomorphous substitutions of host metal ions by foreign ions and other defect states in natural semiconductors altered the band structure, decreased the intrinsic band gap, and then made them very attractive for solar energy utilisation. Our study indicated that natural semiconductor minerals might be suggested as a new class of cost-effective and solar light-responsive photocatalyst.