Phenol is a kind of hardly degradable organic pollutants which widely exist in wastewater and pose great harm to human. In this paper, photocatalytic degradation of phenol was investigated using natural rutile TiO2 powders from Shanxi Province under irradiation of UV and sunlight. The effects of irradiation time, pH value, initial concentration of phenol and dosage of H2O2 on the efficiency of photocatalytic degradation of phenol were studied. The results indicate that natural rutile TiO2, which is commonly thought to have very low catalytic activity, can effectively photodegrade the phenol when it is synergized with H2O2, but the coexistence of light source, charge-trapping agent and photocatalyst is the precondition of photocatalytic reaction.