Volatile　organic　compounds　(VOCs)　are　the　crucial　precursors　to　the　formation　of　fine　particulate　matter　and　photochemical　smog.　Photocatalytic　oxidation　(PCO)　under　vacuum　ultraviolet　(VUV)　irradiation　has　attracted　increasing　interest　for　VOCs　degradation　owing　to　its　strong　oxidation　capability　and　excellent　stability.　However,　the　generation　of　O-3　from　VUV　irradiation　causes　secondary　pollution　and　needs　to　be　addressed.　In　this　study,　the　Mn　doped　mesoporous　TiO2　(Mnimeso-TiO2)　was　developed　and　first　combined　with　VUV　irradiation　to　remove　O-3　as　well　as　enhance　benzene　degradation　via　O-3-assited　catalytic　oxidation.　Results　indicate　that　the　Mn　doped　TiO2　exhibited　a　much　higher　benzene　removal　efficiency　(82%)　than　undoped　one　(70%)　and　commercial　TiO2　P25　(48%).　The　O-3　by-product　can　be　completely　eliminated　by　Mnimeso-TiO2　and　contributed　to　benzene　removal　efficiency　of　about　34%.　The　excellent　performance　was　attributed　to　the　formation　of　highly　reactive　oxidizing　species　such　as　O(D-1),　O(P-3),　hydroxyl　radicals　(center　dot　OH)　via　catalytic　decomposition　of　O-3　over　oxygen　vacancy　sites　of　Mn　oxides.　Mnimeso-TiO2　cooperated　well　with　VUV　and　such　a　VUV-PCO　process　is　very　promising　for　VOCs　degradation.　(C)　2017　Elsevier　B.V.　All　rights　reserved.