Co–Cr–B amorphous catalysts have been synthesized by the chemical reduction method. Catalyst powders were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Brunner-Emmet-Teller measurements (BET). Catalytic performance of the catalyst was measured by the hydrolysis rate of the sodium borohydride solution. Results showed that the particle size of the catalyst was reduced with the addition of a small amount of Cr. The specific surface area increased significantly, and the performance of the catalyst was improved. However, excess addition of Cr caused excess oxides and Cr3+, covering the surface active sites of the catalyst, which degraded the performance of the catalyst. When the ratio of Cr/Co is 0.005, the catalyst performance was optimal and showed nearly 2 times higher H2 generation rate than that of pure Co–B catalyst. In addition, the effect of catalyst content, NaBH4 concentration, reaction temperature, and NaOH concentration on the hydrogen generation of NaBH4 solution was also studied.