Based on the study of equilibrium adsorption on viscose rayon-based activated carbon fiber (ACF) by gravimetric method, mounting of TiO2 on PAN-based activated carbon cloth (ACC) and their photocatalytic activity as well as adsorption performance for benzene were investigated. The crystallinity of TiO2 and pore structure were characterized by XRD and N2 adsorption. The results show that crystallinity of TiO2 and pore structure could be postulated by heat treatment condition. Both crystallinity of TiO2 and pore structure of hybrid have effects on photocatalytic performance of TiO2-mounted ACC. It would be more attractive and prospective for the combination of TiO2 photocatalytic activity and adsorption ability of porous materials.