Solar-driven　photocatalytic　CO2　reduction　receives　intensive　attention　while　facing　the　challenge　of　achieving　a　single　product　with　high　conversion　efficiency.　Herein,　we　report　a　feasible　strategy　for　regulating　isolated　dualmetal　sites　on　semiconductive　metal-organic　frameworks　(MOFs)　for　efficient　CO2　photoreduction.　The　atomically　isolated　CuM　dual-metal　(M　=　Co,　Ni,　Fe)　sites　on　two-dimensional　CuM-THQ　(THQ　=　tetrahydroxyquinone)　with　high　activity　are　obtained.　Impressively,　the　CuCo　dual-metal　sites　present　a　CO　production　rate　of　1626　mu　mol　g-　1　h-　1　and　near　100　%　selectivity　under　visible-light　irradiation.　The　presence　of　Co　sites　induces　the　metal-to-metal　charge　transfer　(MMCT)　process　in　CuM　dual-metal　sites,　enabling　the　extension　of　charge　separation　distance　and　thereby　accelerating　reacting　kinetics.　Moreover,　the　declined　3d-orbital　occupancy　on　CuCo　dual-metal　sites　facilitates　CO2　adsorption　and　reduces　the　energy　barrier　of　the　rate-determining　step　(*CO2　to　*COOH).　Meanwhile,　the　isolated　Cu　sites　provide　a　weak　desorption　of　*CO　intermediates　to　produce　exclusive　CO.　As　a　result,　the　synergist　effect　of　isolated　dual-metal　sites　on　MOFs　contributes　to　the　high　performance　of　CO2-to-CO.