Phenol is a kind of hardly degradable organic pollutants which widely exist in wastewater and pose great harm to human environment, so the decontamination of phenol is an urgent task in China. 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. The degradation efficiency of phenol is much higher in acidic condition than in neutral or alkaline conditions, especially when the pH value is 3.5. When the initial concentration is lower, the phenol can be degraded more completely. When the initial concentration is 60mg/L, the degradation rate is up to 1.922 mg/(L·h). As an effective charge-trapping agent, H2O2 can inhibit the recombination of electron-hole and facilitate the degradation process, and its favorable dosage is 2 ml/L. It is shown that 87.68% of phenol is degraded under sunlight irradiation by natural rutile in 7 h, which iscomparable with the P25 (99.72%), and phenol can be completely degraded by natural rutile TiO2 in 14h.The result of nitrogen adsorption shows that the Brunauer-Emmett-Teller (BET) specific surface area of rutile is only 0.4696 m2/g,which is by far smaller than that of P25 (44 m2/g). According to EPMA and XRD analysis, it is held that the impurity atoms, such as V and Fe, might induce some response to visible light and greatly enhance the photocatalytic capability of natural rutile. As the most common existing form of TiO2 in nature, rutile can be utilized as photocatalyst to tackle the problem of organic pollution. Compared with synthetic titanium dioxide, it can overcome the shortage of low utilization of solar energy and hence has promising environmental application.