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 3MPa, 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.