A highly durable non-noble metal catalyst like copper for high-temperature methanol steam reforming is necessary for a compact hydrogen reactor. Herein, deactivation of copper-based catalysts with strong metal-support interaction is extremely sluggish even at 550 °C when using a selective chemical reduction approach paired with various induced activation procedures. The adsorbate methanol could enhance the migration of ZnOx onto the Cu and increase the number and electronic modulation of high-activity CuZn alloy sites. The Zn pre-deposited on the Cu surface induces continuous morphology and structural reorganization of the catalytic surface, which constantly refreshes the catalyst surface. The adsorbate methanol led to abundant CuZn alloy-ZnO synergism, which sped up the dissociation of·H2O and the dehydrogenation of *CH3O in accordance with the density functional theory and, ultimately, exhibited the highest methanol conversion (99.55 %) and hydrogen yield (97.73 %) compared to the hydrogen induction.