A series of Cu/Zn/Al/Zr CO2 hydrogenation to methanol catalysts containing different ratios of Al/Zr were prepared using a co-precipitation procedure. SEM, TEM, and XRD characterization showed that all the catalysts comprised crystallites in a fibrous structure and their Cu/Zn crystallite dispersions were better than that of a commercial (COM) catalyst. It is suggested that the high dispersion and stability of the Cu/Zn crystallites due to the fibrous structure enhanced CO2 hydrogenation, and the added Zr component further improved the catalyst. A 5% Zr addition gave a methanol space time yield 80% higher than that on the COM catalyst.