Cooperatively　integrating　CO2　reduction　half-reaction　with　selective　organic　oxidation　half-reaction　presents　an　attractive　opportunity　to　simultaneously　utilize　photogenerated　holes　and　electrons　to　realize　carbon　neutrality　and　the　production　of　value-added　chemicals.　Herein,　we　report　the　cooperative　photoredox　catalysis　of　tunable　and　efficient　CO2　reduction　to　syngas　paired　with　4-methoxythiophenol　(4-MTP)　oxidation　to　bis(4-methoxyphenyl)　disulfide　(4-MPD)　over　hybrid　CdSe/CdS　quantum　dots　(QDs).　The　strategy　of　constructing　CdSe/CdS　composites　not　only　facilitates　the　efficiency　of　photoinduced　carrier　separation　and　transfer,　improving　the　photoredox　activity　of　two　half-reactions,　but　also　enhances　CO2　activation,　modulating　the　syngas　CO/H2　ratio　varying　from　1:4–5:4.　Mechanistic　studies　have　revealed　that　4-MTP　is　oxidized　by　holes　located　in　CdS　to　generate　hydrogen　protons　and　sulfur-centered　radicals,　and　then　these　radicals　pair　with　each　other　to　form　4-MPD　with　high　selectivity,　while　the　electrons　in　CdSe　interact　with　protons　and　CO2　for　syngas　production.　Furthermore,　the　feasibility　of　applying　CdSe/CdS　QDs　to　the　cooperative　photoredox　catalysis　of　thiols　with　different　substituents　integrated　with　CO2　into　corresponding　disulfides　and　syngas　has　been　demonstrated.　This　work　envisages　the　development　of　QDs-based　heterostructure　catalysts　for　highly　efficient　photocatalytic　co-production　of　syngas　and　value-added　organic　chemicals.　©　2025　Elsevier　B.V.