Coupling　CO2　photoreduction　with　selective　organic　synthesis　offers　a　promising　modus　operandi　to　enable　simultaneous　utilization　of　photogenerated　electrons　and　holes　to　realize　solar　fuels　production　and　chemicals　synthesis.　Herein,　we　report　a　bifunctional　zero-dimensional　cadmium　sulfide　quantum　dots-two-dimensional　titanium　dioxide　nanosheets　(CdS/TNS)　heterostructure　for　photoredox-catalyzed　coupling　of　C–C　bond　synthesis　via　selective　oxidation　of　benzyl　alcohol　with　CO2　photoreduction　to　CO　under　visible　light.　The　compositing　heterointerface　is　beneficial　for　the　adsorption　and　activation　of　CO2,　thereby　promoting　the　photoreduction　of　CO2.　Remarkably,　the　synergistic　interaction　between　CdS　and　TNS　tunes　the　selectivity　of　benzyl　alcohol　oxidation　from　carbonyl　compound　to　the　C–C　coupled　products.　Mechanistic　studies　unveil　that　the　generation　of　C–C　coupled　products　processes　via　key　radical　•CH(OH)Ph　intermediates.　Theoretical　simulations　reveal　that　the　weaker　adsorption　of　•CH(OH)Ph　radical　over　CdS/TNS　than　bare　CdS　contributes　to　the　formation　of　highly　selective　C–C　coupled　products.　The　findings　are　expected　to　offer　instructive　guidance　on　rationally　designing　the　dual-functional　catalysts　with　efficient　photoredox-catalyzed　coupling　reaction　systems　for　integrating　CO2　reduction　with　selective　organic　transformations.　©　2022　Elsevier　B.V.