Methanol,a versatile chemical,fuel additive and potential H2 carrier,has attracted great attention.Despite of the wide industrialization,improvement of Cu-based methanol-synthesis catalysts is highly anticipated.Accordingly,a series of Cu/ZnO/Al2O3 with designed precursor structures were prepared,and its structure-function relationship was investigated to make progress on this area.Results showed the catalyst derived from highly zinc-substituted malachite demonstrated the best catalytic performance in this work.It was found that the well-behaved catalyst possessed relatively high Cu specific surface area and exposed Cu concentration,and the well Cu/ZnO synergy.CuZn alloy was found by In-situ XRD tests,and its effect on the catalyst's thermostability was discussed.Fractional precipitation,which facilitated the Cu2+sub-stitution by Zn2+in malachite lattice,could be an efficient preparation method of the Cu/ZnO/Al2O3 catalyst.