In order to more easily separate TiO₂ photocatalyst from the treated wastewater, TiO₂ film was immobilized on the surface of activated carbon fibers (ACFs) by employing two kinds of coating procedures, dip-coating and hydrothermal treatment. The effects of coating procedures on microstructure of TiO₂-coated ACFs (TiO₂/ACFs), such as morphology, porous property, crystal structure, and light absorption characteristics were investigated in detail. The adhesion property between TiO₂ film and ACFs was evaluated by ultrasonic vibration, and the photocatalytic activity of TiO₂/ACFs was tested by the photocatalytic decoloration of methylene blue solution. The results show that hydrothermal treatment presented many advantages to obtain high-performance TiO₂/ACFs photocatalyst in comparison with dip-coating. Hydrothermal treatment could improve the binding property between TiO₂ films and ACFs, which endowed the as-obtained TiO₂/ACFs photocatalyst with improved reusable performance, and TiO₂/ACFs synthesized by hydrothermal treatment presented higher photocatalytic activity.