Solar-assisted　photothermal　catalysis　is　a　fascinated　picture　of　chemical　and　energy　conversion.　However,　it　is　difficult　to　distinguish　the　nonthermal　effects　due　to　the　thermal　and　nonthermal　tend　to　exhibit　similar　experimental　results.　Here,　we　reported　that　the　CuNi　alloy　deposited　CeO2　(CuNi/CeO2)　with　visible　light　excited　carriers　at　the　interface　can　promote　CO2　reduction　in　the　photothermal　catalysis.　Impressively,　the　CuNi/CeO2　exhibit　different　product　selectivities　in　the　dark　and　visible　light　reactions,　especially　the　light　promoted　the　further　hydrogenation　to　CH4　conversion.　Detailed　experiments　reveal　that　the　hot　electron　transfer　between　plasmon　metal　Cu　and　metal　Ni　under　visible　light　excitation　alters　the　pathway　of　thermal　reduction　while　increasing　surface　hydroxyl　and　oxygen　vacancies　as　CO2　trapping　sites.　The　excessive　H2　activation　under　visible　irradiation　induces　the　deep　reduction　of　CO2　to　CH4,　instead　of　reverse　water　gas　shift.　Combining　with　in-situ　DRIFTS,　quasi-situ　EPR,　H2　pulse　and　DFT　calculations,　the　nonthermal　effects　of　CO2　reduction　is　proposed　over　CuNi/CeO2　with　electrons　transfer　between　Cu　and　Ni　nanoparticles.　©　2023　Elsevier　B.V.