Activated carbon fiber (ACF) was modified by Zn(NO3)2, ZnCl2 and Zn(CH3COO)2), respectively, and then TiO2 was loaded on the modified ACFs. The adsorption and photocatalysis performance were explored through the removal of toluene, and TiO2/ACF-Ac modified by Zn(CH3COO)2) with the best toluene performance was selected. The characterization results indicated that TiO2 was mainly loaded on the surface with large amount of oxygen-containing functional groups in anatase phase. The photoelectric chemical experiment results demonstrated that the modified ACFs remarkably improved the charge transmission and the separation efficiency of electrons and holes, and enhanced the utilization rate of sunlight. The adsorption saturation time reached 40 hours and photodegradation rate was 70%. The direct desorption of generated small molecule substances such as H2O and CO2 from the surface of the composites can achieve the in-situ regeneration of the adsorbent. Overall, the bifunctional catalysts provide a prospective way for the treatment of VOCs.