Volatile organic compounds (VOCs) exists ubiquitously in chemical industries and were regarded as major contributors to air pollution, which should be strictly regulated. Vacuum ultraviolet irradiation coupled with photocatalytic oxidation (VUV-PCO) has been considered as an efficient approach to VOCs removal due to high-energy photons which could break down VOCs directly and be absorbed by photocatalysts to generate free radicals for further oxidation. However, the photochemical transformation mechanisms of VOCs have not been fully revealed. Herein, we systematically analyzed the intermediates using proton-transfer-reaction mass spectrometer (PTR-MS) to explore the transformation mechanisms of toluene degradation in VUV and VUV-PCO processes. VUV-PCO process displayed superior toluene degradation efficiency (50 %) and mineralization efficiency (65 %) compared with single VUV photolysis (35 %) and UV photocatalysis (5 %). TiO2 was deeply involved into CO2 generalization by amplifying the advantages of VUV system and further mineralizing the intermediates. In VUV and VUV-PCO processes, O2 participation changed the intermediates distribution by increasing multiple oxygenated products, while the introduction of water contributed to the formation and degradation of most intermediates. A possible degradation mechanism of toluene under VUV irradiation combined with TiO2 was proposed. This study provides a deep mechanistic insight into VOCs degradation by VUV-PCO process.