ZrAl materials with different compositions have been synthesized by the hydrothermal method and used as supports of Cu catalysts for hydrogen production from methanol steam reforming (MSR). The effect of the support composition, Zr/Al ratio, on the physicochemical and catalytic properties of CuZrAl catalysts was studied. The characterization results show that there is an optimal support composition (Zr/Al ratio of 0.4), allowing to achieve the highest methanol conversion due to enhanced dispersion and reducibility of copper. Zr-rich catalysts displayed low MSR activity, which is likely due to the segregation and crystallization of zirconia, resulting in the formation of large copper particles with lowered dispersion and reducibility. The catalyst with the optimal Zr/Al ratio shows the highest methanol conversion, enhanced selectivity and good long term stability, rendering this catalyst a promising material for the production of high purity H2 from MSR.