Degradation kinetics and pathway of acetaminophen (APAP) on anatase TiO2, rutile TiO2 and anatase-rutile mixed TiO2 were investigated at UVC 254 nm and UVA 366 nm in a wide photon flux region in the present work. Hydroxyl radicals (center dot OH) induced hydroxylation is the predominant pathway for the degradation of APAP on anatase or anatase containing TiO2 particularly under UVC irradiation, which accounted for more than 50% of total degradation. Valance band hole (h(VB)) induced one electron oxidation contributed approximately 70% of the degradation of APAP on rutile TiO2 under UVA 366 nm irradiation, while direct photolysis contributed more than rutile TiO2 photocatalysis under UVC 254 nm irradiation because of competition for irradiation photon between APAP and rutile TiO2. These results showed that contribution of center dot OH and h(VB) on anatase TiO2 is independent of irradiation photon energy, while irradiation photon energy significantly influences the contribution of center dot OH, h(VB) and direct photolysis to the degradation of APAP on rutile or rutile containing TiO2. Therefore, degradation patterns of APAP and maybe other phenols in TiO2 photocatalysis process could be controlled through changing irradiation photon energy and TiO2 crystalline, which will make TiO2 photocatalysis a selective oxidation system.