Methanol　synthesis　via　CO2　conversion　is　a　“green　carbon”　route　for　mitigating　the　greenhouse　effect　and　recycling　carbon　resources.　However,　despite　the　widespread　use　of　copper-based　systems　for　methanol　synthesis　in　recent　decades,　the　chemical　state　of　the　active　Cu　species　remains　controversial.　In　this　study,　various　Cu/ZnO/SBA-15　catalysts　possessing　different　interfacial　structures　were　engineered　by　atomic　layer　deposition　(ALD).　The　optimized　Cu/50c-ZnO/SBA-15　afforded　the　highest　mass-specific　methanol　formation　rate　of　211.7　gMeOH·kgcat−1·h−1　under　the　conditions　of　250　°C　and　3.0　MPa.　In-depth　characterizations　indicated　that　the　electronic　state　of　Cu　could　be　modulated　by　engineering　the　interfacial　structures　of　the　Cu/ZnO　series　catalysts,　and　the　Cu　cation　sites　(Cuδ+　and　Cu+)　are　the　active　centers　for　methanol　synthesis　reaction　rather　than　the　Cu0　sites.　Mechanistic　analysis　demonstrated　that　HCO3*　and　CO3*　were　slowly　transformed　to　HCOO*　and　further　hydrogenated　to　methanol　following　the　formate-methoxy　intermediate　route.　This　work　provides　an　improved　understanding　of　the　origin　of　the　methanol　synthesis　active　centers　and　emphasizes　the　potential　for　fabricating　next-generation　Cu-based　catalysts　via　ALD.　©　2025　The　Authors