The　structures　and　electronic　properties　of　different　Co　2P-supporting　configurations　on　the　rutile　TiO2(110)　surface　have　been　investigated　by　first-principles　density　functional　theory　(DFT)　calculations.　A　number　of　possible　structural　candidates　and　adsorption　sites　have　been　considered,　while　the　calculations　are　executed　on　periodic　systems　using　slab　model.　Our　results　indicate　that　the　O　atoms　on　TiO　2(110)　turn　out　to　be　preferable　for　the　cluster　to　adsorb　by　Co　atoms,　with　the　largest　adsorption　energy　of　211.50　kJ/mol　in　the　most　favorable　model.　According　to　the　Mulliken　charge　analysis,　the　Co2P　cluster　carries　a　significant　positive　charge　after　adsorption,　due　to　the　charge　transfer　occurring　from　the　adsorbate　to　the　substrate.　Moreover,　the　frontier　molecular　orbital　analysis　shows　that　the　cluster-surface　binding　occurs　mostly　through　the　interplay　of　filled　Co　3d　orbital　with　unoccupied　eigenstates　of　surface　localized　on　O　2p　orbital,　which　can　be　also　corroborated　by　the　projected　density　of　states　investigations,　while　the　lowest　unoccupied　molecular　orbital　is　mostly　contributed　by　Ti　3d　orbital　of　the　surface.　In　addition,　of　particular　significance　is　that　deposition　of　Co2P　on　the　rutile　TiO2(110)　surface　results　in　a　small　band　gap　narrowing　vis-à-vis　the　pure　surface,　yielding　a　positive　effect　on　catalytic　activity.　©　World　Scientific　Publishing　Company.