Introducing　a　new　metal　into　the　metal　center　of　metal–organic　framework　materials　(MOFs)　to　alter　their　original　electron　transfer　pathway　to　improve　photocatalytic　performance　is　a　promising　approach　at　present.　Here,　we　report　a　one-pot　method　to　introduce　Ni2+　into　the　metal-centered　Zr-O　clusters　of　UiO-66-NH2　(UN)　to　create　a　series　of　Ni2+-doped　bimetallic　materials　(xNi-UN).　Experimental　results　showed　that　the　0.5Ni-UN　exhibited　the　highest　photocatalytic　CO2　reduction　activity,　with　a　CO　yield　of　9.01　µmol　g-1h−1　under　visible　light　irradiation,　which　was　2.46　times　higher　than　that　of　UN　(3.67　µmol　g-1h−1).　Through　a　number　of　characterization　analyses,　we　find　that　the　doped　Ni2+　replaced　the　part　of　original　metal　center　Zr4+　to　form　a　bimetallic　UiO-66-NH2　(Zr/Ni),　which　changed　the　energy　band　gap　of　UiO-66-NH2　and　improved　the　charge　transfer.　More　importantly,　the　introduction　of　Ni2+　enhanced　the　efficiency　of　interfacial　charge　transfer　from　the　organic　ligand　(2-aminoterephthalic　acid)　to　the　Zr-O　cluster,　enabling　a　metal-to-metal　charge　transfer　(MMCT)　pathway,　which　exhibited　higher　photocatalytic　CO2　to　CO　reduction　activity.　©　2024　Elsevier　B.V.