Solar-driven　CO2　reduction　integrated　with　C−C/C−X　bond-forming　organic　synthesis　represents　a　substantially　untapped　opportunity　to　simultaneously　tackle　carbon　neutrality　and　create　an　atom-/redox-economical　chemical　synthesis.　Herein,　we　demonstrate　the　first　cooperative　photoredox　catalysis　of　efficient　and　tunable　CO2　reduction　to　syngas,　paired　with　direct　alkylation/arylation　of　unactivated　allylic　sp3　C−H　bonds　for　accessing　allylic　C−C　products,　over　SiO2-supported　single　Ni　atoms-decorated　CdS　quantum　dots　(QDs).　Our　protocol　not　only　bypasses　additional　oxidant/reductant　and　pre-functionalization　of　organic　substrates,　affording　a　broad　of　allylic　C−C　products　with　moderate　to　excellent　yields,　but　also　produces　syngas　with　tunable　CO/H2　ratios　(1　:　2–5　:　1).　Such　win-win　coupling　catalysis　highlights　the　high　atom-,　step-　and　redox-economy,　and　good　durability,　illuminating　the　tantalizing　possibility　of　a　renewable　sunlight-driven　chemical　feedstocks　manufacturing　industry.　©　2023　Wiley-VCH　GmbH.