Photothermal　catalytic　conversion　of　CO2　to　high　valuable　chemicals　is　a　promising　technology　to　meet　carbon　neutrality　strategy,　photothermal　synergy　can　enhance　catalyst　activities　for　photothermcatalytic　CO2　reduction　with　H2O　vapor.　In　this　paper,　ZrO2/ZnS　catalysts　with　different　ratios　have　been　fabricated　by　the　simple　hydrothermal　method,　exhibiting　improved　charge-carrier　separation　efficiency　and　increased　vacancies.　The　physicochemical　properties　of　the　catalysts　such　as　crystal　structures,　morphologies,　adsorption　capacity,　optical　and　electronic　properties　were　investigated.　The　x-ZrO2/ZnS　composites　possess　improved　activity　for　CO2　reduction,　mainly　due　to　the　promoted　S　vacancy　concentration　and　the　photothermal　synergy　effect.　The　optimal　catalyst　45-ZrO2/ZnS　exhibits　CO　generation　rate　of　9.4　mu　mol/g/h,　which　was　significantly　higher　than　that　of　the　pure　ZrO2　and　ZnS.　Moreover,　the　possible　reduction　pathways　and　reaction　intermediates　were　further　studied　by　in　situ　DRIFT.　The　present　work　provides　a　simple　strategy　to　develop　photothermal　catalysts　for　CO2　conversion　with　water　vapor.