Micro-reactors for the preferential oxidation of CO in H₂-rich stream (CO-PROX) are attractive for PEMFCs employed in portable electronic devices and automobiles, but the jolt is inevitable, which makes micro-reactors necessitate high jolt resistance. The monolithic structured catalyst could effectively resolve these problems. Herein, we employed the thin-felt monolithic Al-fiber substrate to fabricate the CuO–CeO₂/AlOOH/Al-fiber catalyst for the CO-PROX reaction. This catalyst was prepared via first growing AlOOH nanosheets onto the Al-fiber surface by steam oxidation method, followed by depositing CuO–CeO₂ onto the AlOOH/Al-fiber support. The preferred catalyst delivered 100% CO conversion and 81% O₂ selectivity at 140 °C with a gas hourly space velocity of 12,000 mL g⁻¹ h⁻¹, and particularly, performed stably for 120 h at the changeable temperatures of 120–160 °C. This work provides a strategy to tailor a qualified monolithic catalyst that couples the promising jolt resistance and catalytic performance at 120–160 °C.