Moisture-resistant TiO2-based catalysts with high activity and stability are urgently needed to satisfy requirements for the treatment of volatile organic compounds (VOCs). In this work, a novel hydrophobic F-doped carbon-wrapped TiO2 catalyst (TiO2 @HFC) was synthesized by a facile method and used for the photocatalytic degradation of toluene. TiO2 @HFC displays significantly higher activity under UV/Vis irradiation than commercial P25 TiO2, and remains stable after six cycles. The removal efficiency of toluene was 81.7% after 210 min of reaction, corresponding to a mineralization efficiency of 74.5%. Benefiting from the hydrophobic F-doped carbon layer modification, the incorporation of F into TiO2 crystals, and increased Ti3+ content, TiO2 @HFC is characterized by efficient separation and utilization of photoexcited charge carriers, enhanced adsorption of toluene, and robust resistance towards water vapor. This work demonstrates the potential application of the TiO2-based photocatalyst to efficiently remove VOCs in a humid environment.