Titanium　dioxide　(TiO2)　alone　is　rarely　reported　to　have　exciting　performance　towards　heterogeneous　hydrogenation　reactions.　In　this　work,　we　demonstrateviadensity　functional　theory　(DFT)　calculations　that　anatase　TiO2with　oxygen　vacancies　(Ovs),　which　provides　frustrated　Lewis　pairs　(FLPs)　from　surface　Ti　and　O　atoms　for　the　heterolytic　dissociation　of　hydrogen,　can　effectively　hydrogenate　acetylene　to　ethylene.　Meanwhile,　the　mechanisms　of　H2activation　and　acetylene　hydrogenation　with　several　structure-reactivity　correlations　are　well　established,　suggesting　the　potential　catalytic　reactivity　in　the　presence　of　Ovs　on　anatase　TiO2surfaces.　Then,　the　reactivity　of　anatase　TiO2towards　acetylene　hydrogenation　is　preliminarily　confirmed　by　experimental　studies　which　show　that　the　existence　of　Ovs　after　reduction　leads　to　higher　reactivity.　These　results　can　provide　important　implications　for　the　further　development　of　selective　hydrogenation　catalysts　based　on　earth-abundant　materials.　©　The　Royal　Society　of　Chemistry　2021.