Co/Al 2 O 3 catalyst is prepared with an impregnation-chemical reduction method and used to catalyze the methanolysis of sodium borohydride (NaBH 4 ) for hydrogen generation. At solution temperature of 0 °C, the methanolysis reaction can be effectively accelerated using Co/Al 2 O 3 catalyst and provide a desirable hydrogen generation rate, which makes it suitable for applications under the circumstance of low environmental temperature. The byproduct of methanolysis reaction is analyzed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The characterization results indicate that methanol can be easily recovered after methanolysis reaction by hydrolysis of the methanolysis byproduct, NaB(OCH 3 ) 4 . The catalytic activity of Co/Al 2 O 3 towards NaBH 4 methanolysis can be further improved by appropriate calcination treatment. The catalytic methanolysis kinetics and catalyst reusability are also studied over the Co/Al 2 O 3 catalyst calcined at the optimized temperature.