Cu/ZnO/Al2O3　catalysts　have　been　widely　applied　as　industrial　catalysts　for　methanol　synthesis　from　syngas,　but　suffers　low　activity　for　CO2　hydrogenation　to　methanol.　This　study　establishes　highly　active　Cu　catalysts　through　modulation　of　the　composite　of　Al2O3　and　ZrO2　in　Cu/ZnO-based　catalysts.　The　composition　of　Al2O3　and　ZrO2　impacts　the　Cu　dispersion,　exposed　surface　area　of　Cu,　the　Cu0/(Cu0+Cu+)　ratio　and　surface　basicity.　An　appropriate　content　of　Al2O3　and　ZrO2　presents　the　higher　Cu　surface　area,　desirable　ratio　of　Cu0/(Cu0+Cu+)　and　moderate-strong　basic　sites　for　effective　CO2　adsorption/activation,　giving　rise　to　higher　space-time　yield　of　methanol　(up　to　648　gCH3OH·kgcat　−1·h−1)　than　the　commercial　Cu　catalyst.　STY　of　methanol　can　be　correlated　with　Cu　surface　area　and　Cu0/(Cu0+Cu+)　ratio　under　the　investigated　conditions.　The　mechanistic　analysis　demonstrates　that　surface　formate　and　methoxy　species　are　the　major　intermediates.　The　methanol　formation　principally　follows　the　formate-methoxy　intermediate　pathway.　©　2024　Elsevier　B.V.