The influence of elemental composition on the crystal structure, hydrogen storage and electrochemical properties for Mg-containing alloys was investigated. As La/Mg ratio decreased, the slight change of Ni content was detected. XRD results indicated that these alloys were composed of LaNi 5 and Mg-containing phases. The lattice parameters of Mg-containing phases decreased. Meanwhile, the mass fraction of Mg-containing phases varied with the change of La/Mg and Ni. The hydrogen storage capacity reached ~1.6 wt.% for La/Mg≧ 3 :1 and decreased to ~0.71 wt.% for La/Mg=1. Two hydrogen absorption processes were observed because of the existence of the multiphases for La/Mg≧ 3 :1. With decreasing La/Mg ratio, the equilibrium pressurerose due to the shrinkage of the lattice parameter. Meanwhile, one hydrogen absorption process was obviously present. The discharge capacity of these as-cast alloys was higher, but the cyclic stability was poor for La/Mg≧ 3 :1 due to the partial amorphisation. It was better for La/Mg≤2 although the discharge capacity was lower. The polarization resistance increased, contrarily the exchange current density decreased with decreasing Mg content.