<p>Photo-thermal synergistic catalysis offers a promising route for low-temperature and efficient hydrogen production, in which the design of catalysts is crucial. In this study, a series of promoter-modified Cu supported on ZnO (M-Cu/ZnO, M = Al, Zr, Co, Ce) were designed and prepared via a controllable hydrothermal synthesis strategy, and their catalytic performance in photo-thermal methanol steam reforming (MSR) for hydrogen production was systematically investigated. By varying the type of promoter, precise modulation of the catalyst's textural properties, metal-support interactions, and distribution of active sites was achieved. Characterization results revealed that the introduction of Al promoters significantly enhanced the dispersion of Cu species on the ZnO surface and strengthened metal-support interactions, thereby effectively suppressing the sintering and deactivation of active components during the reaction. Under photo-thermal MSR conditions of 240&#xa0;°C, 0.1&#xa0;MPa, and a space velocity of 17 300&#xa0;mL·g⁻¹·h⁻¹, the Al-Cu/ZnO catalyst exhibited the optimal catalytic performance, achieving a methanol conversion of 97.08% and an H₂ yield of 99.14&#xa0;mL·g⁻¹·min⁻¹, with only an 11% decrease in conversion after 10&#xa0;h of continuous operation, demonstrating excellent stability. This work elucidates the structure–activity relationships in multicomponent Cu/ZnO catalysts for photo-thermal MSR from the perspective of promoter engineering, providing both experimental evidence and design insights for the development of efficient and stable solar-driven hydrogen production catalyst systems.</p>