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Commercial and laboratory-prepared V2O5-WO3/TiO2-based catalysts with different compositions were tested for catalytic decomposition of chlorobenzene (ClBz) in simulated waste combustion flue gas. Resonance enhanced multiphoton ionisation- time of flight mass spectrometry (REMPI-TOFMS) was employed to measure real-time trace concentrations of ClBz contained in the flue gas before and after use of the catalyst. The results showed that the ClBz decomposition efficiency was significantly enhanced when nano-TiO2 instead of conventional TiO2 was used as the catalyst support. No promotion effects were found in the ClBz decomposition process when the catalysts were wet-impregnated with CuO and CeO2. A comparison between ClBz and benzene decomposition on the V2O5-WO3/TiO2-based catalyst showed that different active sites were likely involved in the decomposition mechanism, and the V=O and V-O-Ti groups may only work to catalyse the degradation of the phenyl group and the benzene ring rather than the C-Cl bond.