Methanol steam reforming (MSR) is considered as an effective way to provide on‐board hydrogen production technology for fuel cell applications. CuFe1.2Al.8O4 spinel catalyst was synthesized by sol–gel method and the chemical and physical properties were studied in‐depth. X‐ray diffraction, hydrogen‐temperature programmed reduction (H2‐TPR), BET, and scanning electron microscopy were used to characterize the catalysts with reaction times of 20, 50, and 100 h. The results of H2‐TPR showed that 90% of spinel Cu2+ was released after 100 h reaction. BET results show that the specific surface area and pore characteristics of the catalyst have not changed greatly after reaction for 20, 50, and 100 h. Furthermore, in the unsteady‐state test, CuFe1.2Al.8O4 exhibited excellent catalytic activity and thermal stability under long‐term repeated start‐up and stop cycles. At 275°C, the methanol conversion rate remained around 94% and the CO selectivity remained below 1%. Therefore, the catalyst synthesized in this study has excellent stability and low CO selectivity, making it a highly promising on‐board hydrogen production catalyst in the field of HT‐proton exchange membrane fuel cells (PEMFCs).