Tailoring　the　metal-oxide　interface　by　atomic　layer　deposition　(ALD)　is　a　promising　strategy　to　modulate　active　sites　for　methanol　synthesis　from　CO2　hydrogenation.　Herein,　specific　Cu/ZnOx/CeO2　interfaces　are　constructed　by　controlling　the　deposition　sequence　and　amount　of　ZnO　in　Cu-Zn-Ce　oxide　catalysts　via　the　ALD　method.　In-depth　characterizations　demonstrate　that　Cu+-Zn0-Ce4+　structure　is　the　active　site　for　methanol　synthesis　from　CO2　hydrogenation.　This　strategy　provides　a　viable　way　to　tune　the　metal-oxide　interface　to　develop　catalysts　and　favors　precise　understanding　of　the　catalytic-structure　activity　relationship　of　the　Cu　species　in　the　process　of　CO2　conversion　to　methanol.　©　2024　The　Royal　Society　of　Chemistry.