The phase of Cu,Zn,Al precursors strongly affects the activity of their final catalysts. Herein, the Cu,Zn,Al precursor was prepared by precipitation of Al3+ onto primitive, amorphous Cu,Zn precipitate. This precursor turned out to be a phase mixture of zincian malachite and hydrotalcite in which the latter phase was less abundant compared to the co-precipitated precursor. The final catalyst derived from this precursor exhibited a little higher copper surface area and methanol synthesis activity than the co-precipitated counterpart. Therefore, the two precursor phases need to be mixed in an adequate proportion for the preparation of active Cu/ZnO/Al2O3 catalyst.