Co-TiO2 catalysts have been synthesized by the sol-gel method, and they were characterized by X-ray fluorescence, Brunauer-Emmett-Teller, scanning electron microscopy, high-resolution transmission electron microscopy, X-ray photoelectron, spectroscopy, and ultraviolet diffuse reflectance spectroscopy technologies. To evaluate the activities of the catalysts, a series of tests have been conducted to decontaminate the phenol simulated wastewater at neutral pH. Because Co-TiO2 represented ability to decompose KHSO5 to generate, sulfate radicals (Co/SR) and visible light photocatalytic activities (photo), we defined them as a type of "bifunctional catalyst". Moreover, the obvious combined effect of Co/SR and photo was also observed. Results indicated that the cobalt species takes a function to integrate sulfate radical based advanced oxidation reaction and the TiO2 photocatalytic process in one heterogeneous system. Under optimum conditions of D-Co(2+) = 1.0%, T-C = 773 K, M-KHSO5/M-phenol = 10.1, and C-cata 1.0 g/L, about 76.2% total organic content removal and 100% degradation of 50.0 mg/L phenol could be achieved after 2 h of hybrid Co/SR photo treatment. Finally, the possible catalytic mechanism of the synergistic system has been proposed.