Owing　to　the　unique　synergistic　effect,　dinuclear-metal-molecule-catalysts　(DMCs)　show　excellent　performance　in　catalytic　fields.　However,　for　overall　photocatalytic　CO2　reaction　(CO2RR),　it　is　still　a　challenge　to　construct　well-matched　photosensitizer　(PS)　components　for　DMCs-based　photocatalysts.　Inorganic-quantum-dot　PS　possesses　capacities　of　multiple　exciton　generation　and　catalyzing　water　oxidation　but　is　incompatible　with　DMCs.　In　contrast,　organic　PS　can　be　covalently　linked　with　DMCs　but　inescapable　of　using　sacrificial　electron　donors.　For　overall　photocatalytic　CO2RR,　organic–inorganic　dual-photosensitizing　system　might　be　a　promising　candidate.　Herein,　we　employed　covalent-linking　and　electrostatic-driven　approaches　to　construct　the　self-assembly　of　pyrene-sensitized　Co2L　DMCs　(Py-Co2L)　and　perovskite　(PVK)　quantum　dots,　i.e.,　PVK@[Py-Co2L].　Using　H2O　as　an　electron　donor,　PVK@[Py-Co2L]　realized　105.24　μmol　⋅　g−1⋅h−1　CO　yield　in　photocatalytic　CO2RR,　much　higher　than　PVK　(15.44　μmol　⋅　g−1⋅h−1)　and　PVK@Co2L　(32.30　μmol　⋅　g−1　⋅　h−1),　ascribing　to　the　efficient　photogenerated　charge　separation　and　transfer.　The　experimental　results　and　theoretical　investigations　demonstrated　that　the　pyrene　linked　on　Co2L　boosted　the　electron　delivery　from　PVK　to　DMCs.　Besides,　this　strategy　could　also　be　extended　to　the　photocatalytic　H2　evolution　coupled　with　alcohol　oxidation.　As　a　proof-of-concept,　our　work　lightens　the　integration　of　DMCs,　organic　and　inorganic　PS　components,　promoting　the　development　of　photocatalysis　without　sacrificial　electron　donors.　©　2024　Wiley-VCH　GmbH.