The high-energy ball-milling technique is generally used to modify the surface structure and texture of materials in order to improve their physical or chemical properties. In the conditions of thermodynamic equilibrium, the hydrogen-storage capacity of Ti0.9Zr0.2Mn1.6Ni0.2V0.2 alloy can reach 240.9 ml/g, from which it can be calculated that its theoretical capacity is 537.3 mA h/g. However, its discharge capacity in KOH solution is only less than 40 mA h/g. In order to improve this capacity, the effect of ball milling with Ni powders on the electrochemical and structural properties of Ti0.9Zr0.2Mn1.6Ni0.2V0.2 alloy was investigated. The results show that proper ball milling with Ni powders is very effective to improve the discharge capacity of the Ti0.9Zr0.2Mn1.6Ni0.2V0.2 alloy by increasing the surface electrocatalytic ability.