The　escalating　emission　of　CO2　has　caused　a　significant　environmental　impact.　Hydrogenation　of　CO2　to　methanol　stands　as　the　primary　objective　in　the　liquid　sunlight　vision,　aiming　to　mitigate　CO2　emissions.　CuZn-based　transition　metal　catalysts,　known　for　their　cost-effectiveness,　demonstrate　commendable　catalytic　performance　at　moderate　temperatures　and　pressures,　showcasing　considerable　potential　in　industrial　applications.　Consequently,　a　series　of　catalysts,　composed　of　CuZn-based　species　supported　on　CeO2　with　strategically　introduced　appropriate　oxygen　vacancies,　were　meticulously　prepared.　It　worth　to　noting　that　the　size　of　Cu　was　precisely　tuned,　along　with　the　enhanced　ability　to　the　adsorption　and　activation　of　CO2　and　H2.　As　a　result,　the　optimal　CuZn/CeO2　catalyst　exhibits　high　methanol　formation　rate,　recording　at　433.4　gMeOH　kgcat−1　h−1　with　selectivity　of　68.5%　at　260　°C　and　3　MPa.　Simultaneously,　the　reaction　path　and　the　evolution　of　intermediates　in　CO2　hydrogenation　was　thoroughly　delineated.　©　2024