CO2　hydrogenation　to　CH3OH　is　of　great　significance　for　achieving　carbon　neutrality.　Here,　we　show　a　urea-assisted　grinding　strategy　for　synthesizing　Cu-Zn-Ce　ternary　catalysts　(CZC-G)　with　optimized　interfacial　synergy,　achieving　superior　performance　in　CO2　hydrogenation　to　methanol.　The　CZC-G　catalyst　demonstrated　exceptional　methanol　selectivity　(96.8%)　and　a　space-time　yield　of　73.6　gMeOHkgcat-1h-1　under　optimized　conditions.　Long-term　stability　tests　confirmed　no　obvious　deactivation　over　100　h　of　continuous　operation.　Structural　and　mechanistic　analyses　revealed　that　the　urea-assisted　grinding　method　promotes　the　formation　of　Cu/Zn-Ov-Ce　ternary　interfaces　and　inhibits　the　reduction　of　ZnO,　enabling　synergistic　interactions　for　efficient　CO2　activation　and　selective　stabilization　of　formate　intermediates　(HCOO*),　which　are　critical　for　methanol　synthesis.　In-situ　diffuse　reflectance　infrared　Fourier　transform　spectra　and　X-ray　absorption　spectroscopy　studies　elucidated　the　reaction　pathway　dominated　by　the　formate　mechanism,　while　suppressing　the　reverse　water-gas　shift　reaction.　This　work　underscores　the　critical　role　of　synthetic　methodologies　in　engineering　interfacial　structures,　offering　a　strategy　for　designing　high-performance　catalysts　for　sustainable　CO2　resource　utilization.　(c)　2025,　Dalian　Institute　of　Chemical　Physics,　Chinese　Academy　of　Sciences.　Published　by　Elsevier　B.V.　All　rights　reserved.