The electrochemical properties of amorphous MgNi-based hydrogen storage alloys synthesized by mechanical alloying (MA) were evaluated. The results show that these amorphous Mg50Ni50 alloys exhibit a higher discharge capacity and relatively good rate capacity at a suitable grinding time while their cycle life is very poor. In order to improve the cycle life, the surface of the amorphous Mg50Ni50 alloy was coated with Ti, Al and Zr in Spex 8000 mill/mixer and the coating effects were further investigated. Based on experimental results, two kinds of MgNi-based amorphous alloys are designed by substituting part of Mg in MgNi-based alloys by suitable elements. These alloys are then composed of four components. Thus, the cycle life of electrodes consisting of these quaternary amorphous alloys is greatly improved.