Regulation　of　abundant　Cu-ZnO　interfaces　in　Cu/ZnO　catalysts　is　critical　to　the　thermal　hydrogenation　of　CO2　to　methanol.　Herein,　Cu-ZnO　interfaces　were　precisely　regulated　by　depositing　thin　ZnO　films　on　copper　phyllosilicates　(CuSiO3)　through　atomic　layer　deposition　(ALD)　to　prepare　Cu/ZnO/SiO2　composite　catalysts　(denoted　as　xZnO/CuSiO3,　x　is　the　number　of　ALD　cycles)　for　CO2　hydrogenation　to　methanol.　Interestingly,　5ZnO/CuSiO3　exhibited　much　higher　methanol　selectivity　of　68.1　%　and　methanol　space-time　yield　(STYMeOH)　of　0.39　gMeOH　h−1gcat−1　toward　CO2　hydrogenation　at　275　℃　and　3　MPa,　as　compared　to　the　pristine　CuSiO3　(38.1　%　and　0.24　gMeOH　h−1gcat−1),　suggesting　the　significant　role　of　Cu-ZnO　interfaces.　Compared　to　ZnO/CuSiO3(IM)　prepared　by　the　conventional　impregnation　method,　5ZnO/CuSiO3　possessed　much　higher　CO2　conversion　(13.8　%　vs.　10.1　%)　and　methanol　selectivity　(68.1　%　vs.　56.2　%).　Furthermore,　the　catalytic　activities　of　the　prepared　Cu/ZnO　catalysts　can　be　effectively　regulated　by　changing　the　thickness　of　ZnO-ALD　films,　in　which　5ZnO/CuSiO3　showed　the　best　catalytic　activity.　Various　characterization　methods　were　applied　to　demonstrate　that　ALD-ZnO　was　evenly　laid　flat　on　the　surface　of　CuSiO3　to　construct　abundant　Cu-ZnO　interfaces　during　the　H2　reduction　treatment,　which　facilitated　the　dissociated　activation　of　CO2　and　formation　of　CH3O*　reaction　intermediate　and　simultaneously　inhibited　the　generation　of　CO　byproduct.　In　addition,　the　density　functional　theory　(DFT)　calculations　revealed　the　stronger　interaction　between　Cu　and　ZnO　over　5ZnO/CuSiO3,　which　implied　more　Cu-ZnO　interfaces　were　generated　for　methanol　production.　Accordingly,　this　study　verifies　the　significance　of　Cu-ZnO　interfaces　for　CO2　hydrogenation　to　methanol　and　provides　a　facile　method　to　regulate　Cu-ZnO　interfaces　by　depositing　ALD-ZnO　films　on　the　copper　phyllosilicate　precursor.　©　2024　Elsevier　B.V.