The structure and electrochemical hydrogen storage properties of the ball-milled LaMg 10 Ni 2 alloys with Ni powder in the range of 50, 100 and 150wt.%, respectively, were investigated. It was found that the amount of Ni addition was a key factor influencing the electrochemical properties. The amorphous (LaMg 10 Ni 2 + 150wt.% Ni) composite exhibited a high discharge capacity of 832mAh/g. The effect of partial substituted Al for Ni in the LaMg 10 Ni 2 alloys on the electrochemical properties was also studied. The experimental results showed that the amorphous-like (LaMg 10 NiAl + 150wt.% Ni) composite exhibited the highest discharge capacity of 953mAh/g, corresponding to a hydrogen storage capacity of 3.56wt.%. The Al substitution for Ni in the LaMg 10 Ni 2 alloys had a positive effect on the hydrogen storage capacity. But, the cycling stability needs to be improved when they are to be considered as electrode materials. The reason why the ball-milled (LaMg 10 NiAl + 150wt.% Ni) composite had the highest hydrogen storage capacity was analyzed by powder X-ray diffraction (XRD) and electrochemical impedance spectra (EIS). The existence of a second phase (AlNi) in the LaMg 10 NiAl alloy probably plays an important role in the improvement of the catalytic activity and the electrochemical properties.