Constructing　dual　single-atom　catalysts　with　distinct　electronic　structures　holds　significance　for　the　design　of　catalytic　active　centers,　yet　it　remains　highly　challenging.　Here,　a　novel　light-induced　approach　was　created　to　construct　Ni0　and　Niδ+　dual　single-atom　sites　on　ZnIn₂S₄　nanosheets　(Ni0-Niδ+/ZIS)　for　the　photocatalytic　reduction　of　CO₂.　Characterizations　and　density　functional　theory　(DFT)　calculations　results　indicate　that　Niδ+　and　Ni0　single-atom　sites　can　be　selectively　anchored　in　the　Zn　vacancies　and　lattice　interstitials　on　the　surface　of　ZIS,　respectively.　Ni0　atoms　are　in　a　low-spin　state　without　unpaired　electrons.　In　contrast,　Niδ+　atoms　are　in　an　intermediate-spin　state　with　an　unpaired　electron,　which　can　be　migrated　from　the　3d　orbital　of　Nδ+　to　the　2πu　orbitals　of　CO₂.　Niδ+　and　Ni0　sites　decouple　the　competitive　pathways　of　CO₂　reduction　and　H₂　evolution　via　distinct　adsorption　of　H₂O　and　CO₂　on　Ni0　or　Niδ+　sites　(ΔG　＞　0.5　eV),　respectively.　Ni0　sites　facilitate　the　generation　of　H₂　from　H₂O,　whereas　Niδ+　sites　preferentially　reduce　CO₂　to　CO.　Furthermore,　the　Ni0-Niδ+　dual　single-atom　sites　significantly　enhance　the　efficiency　of　charge　separation　and　transfer.　Therefore,　the　catalyst　attains　a　high　syngas　yield　of　58.66　mmol·g−1·h−1　under　visible　light,　with　adjustable　CO/H₂　ratios　from　1:1.3　to　1:4.1.　This　work　presents　a　promising　light-induced　strategy　for　constructing　dual　single-atom　catalysts　via　modulating　metal　electronic　structure.　©　2025　Elsevier　Inc.