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.