The　direct　synthesis　of　ethanol　from　syngas　is　a　promising　way　in　the　field　of　clean　and　efficient　use　of　fossil　fuel,　but　it　still　suffers　from　insufficient　ethanol　selectivity　and　understanding　of　active　sites.　In　this　work,　the　Rh-based　catalyst　with　Ce　as　promoter　and　ZrO2　as　carrier　exhibits　excellent　catalytic　performance,　showing　the　selectivity　of　ethanol　toward　24.3　%.　Moreover,　the　yield　of　methane　decreases　to　4.8　%,　and　the　formation　of　CO2　is　inhibited　to　a　certain　degree　by　tuning　the　active　sites.　The　carrier　is　changed　by　doping　Ce　into　the　ZrO2　lattice,　which　assists　to　form　the　Rhδ+　active　sites.　The　synergetic　effect　of　Ce　and　Zr　is　important　to　influence　the　state　of　Rh　species　in　the　catalysts,　leading　to　the　differences　in　the　CO　hydrogenation　process.　On　the　other　hand,　the　Rhδ+　active　sites　are　also　stabilized　by　promoted　surface　oxygen　vacancies　in　the　2.0Rh5.0Ce-ZrO2　catalyst.　The　high-activity　catalyst　with　Rhδ+　active　sites　will　be　helpful　to　understand　the　real　active　sites　of　Rh-based　catalysts　for　ethanol　synthesis　from　syngas,　thereby　guiding　further　design　of　the　related　catalyst　with　high　performance　to　meet　the　industrial　demand　in　syngas　converting　to　ethanol.　©　2022　Elsevier　Ltd