Localized　surface　plasmon　resonance　(LSPR)　on　base-metal　nanoparticles　holds　significant　potential　for　applications　in　diverse　fields　owing　to　its　capability　for　electric　field　enhancement.　Nevertheless,　the　efficiency　of　single-energy　conversion　remains　a　limiting　factor　for　LSPR　applications.　This　study　investigated　the　utilization　of　hot　carriers,　generated　through　the　LSPR　effect　in　copper　nanoparticles　(Cu　NPs)　supported　on　ZrO2,　to　enhance　the　performance　of　the　thermal　catalytic　reverse　water-gas　shift　(RWGS)　reaction.　Finite　difference　time　domain　simulations　and　Kelvin　probe　force　microscopy　(KPFM)　tests　demonstrated　that　LSPR　induces　a　strong　electric　field,　facilitating　the　excitation　of　hot　carriers　in　Cu　NPs.　In-situ　DRIFTS　analysis　revealed　that　hot　electrons　promote　the　formation　of　formate　species　(HCOO*)　and　their　subsequent　transformation　into　CO,　identified　as　the　rate-determining　step.　Furthermore,　in-situ　H2　pulse　and　quasi-in　situ　EPR　analyses　indicated　that　photo-assisted　thermal　conditions　enhance　the　conversion　of　H2　into　active　hydrogen　species　(H*　or　H　+　)　on　Cu　NPs,　promoting　the　generation　of　oxygen　vacancies　and　the　transformation　of　intermediates.　Constrained　density　functional　theory　calculations　further　demonstrated　that　visible　light　irradiation　reduces　energy　barriers,　thereby　increasing　reaction　efficiency.　The　findings　provide　valuable　insights　into　the　contribution　of　LSPR-induced　hot　electrons　in　advancing　the　RWGS　reaction.