Ultra-thin (1-3 cationic-layers) (CuZn)1-xGax-CO3 layered double hydroxides (LDH) nanosheets were synthesized following the aqueous miscible organic solvent treatment (AMOST) method and applied as catalyst precursors for methanol production from CO2 hydrogenation. It is found that upon reduction, the aqueous miscible organic solvent treated LDH (AMO-LDH) samples above a critical Ga 3+ composition give consistently and significantly higher Cu surface areas and dispersions than the catalysts prepared from conventional hydroxyl-carbonate phases. Owing to the distinctive local steric and electrostatic stabilization of the ultra-thin LDH structure, the newly formed active Cu(Zn) metal atoms can be stably embedded in the cationic layers, exerting an enhancement to the catalytic reaction. The best catalyst in this study displayed methanol productivity with a space-time yield of 0.6 gMeOH•gcat-1 •h-1 under typical reaction conditions, which as far as we are aware, is higher than most reported Cu-based catalysts in the literature.