Abstract: Cu-Ni-Al ternary spinel solid solution catalysts with different Al content are prepared by the solid-phase ball milling method. The characterizations with XRD, H₂-TPR, BET and XPS, and catalytic performance testing are carried out to study the effects of Al content on the physicochemical properties of the Cu-Ni-Al spinels and their sustained release catalytic performances in methanol steam reforming for hydrogen production. Characterization results show a significant increase in the specific surface area and pore volume of the catalysts with increasing the Al content (Al = 2, 3, 4) at a constant Cu/Ni molar ratio of 0.95:0.05. At the same time, both the cell parameters and crystallite sizes of Cu-Ni-Al spinel solid solutions decrease, and the catalysts become difficult to be reduced. Furthermore, the content of spinel Ni²⁺ increases slightly while the spinel Cu²⁺ decreases significantly, leading to a declined total content of spinel Cu²⁺ plus Ni²⁺. The results also indicate that the presence of Ni²⁺ inhibits the formation of spinel Cu²⁺. Surface analysis results show that the increase of Al content transforms the catalyst surface composition from Cu-rich to Al-rich, and the surface spinel Cu²⁺ decreases, but it is still higher than the spinel bulk. The catalyst testing results show that as the Al content in the catalysts increases, the initial activity increases notably, and the CO selectivity decreases, but too much Al results in an inferior catalytic stability. In general, the catalyst with an Al = 3 shows a better catalytic performance in terms of activity and stability. The results of this paper demonstrate that there is an optimal Al content for the Cu-Ni-Al spinel solid solutions used as the sustained release catalysts, playing a crucial role in obtaining high catalytic stability.