Structure and electrochemical properties of (La, Ce, Pr, Nd)_2MgNi_9 hydrogen storage alloys were investigated through orthogonal design experiments, and the alloys were obtained through induction melting followed by annealing treatment. The structure of main phase in alloys belongs to PuNi_3-type with a space group R3m. Rare earth elements, as a substitute of lanthanum, have a significant effect on phase structure of alloys, elements of cerium and neodymium are beneficial to the formation of Gd_2Co_7-type phase with a space group P 6_3/mmc. Rare earth elements can decrease the unit cell volume of main phase of alloys dramatically, and increase the axis ratio. The results of electrochemical experiment showed that the discharge capacity of alloy electrodes ranged from 342.97 to 380.68 mAh·g -1, and elements of cerium and neodymium can reduce the discharge capacity of alloy electrodes significantly. Compared to the electrode of La_2MgNi_9 alloy, the substitution of lanthanum by rare earth elements did not improve the cyclic stability of alloy electrodes due to the anisotropic structure change of unit cell. While rare-earth elements can improve the high rate dischargeability of alloy electrodes, the high rate dischargeability of alloy electrodes could reach the maximum when the unit cell volume of PuNi_3-type structure was about 0532 nm. Structure and electrochemical properties of (La, Ce, Pr, Nd) _2MgNi_9 hydrogen storage alloys were investigated through orthogonal design experiments, and the alloys were obtained through induction melting followed by annealing treatment. The structure of main phase in alloys belongs to PuNi_3-type with a space group R3m. Rare earth elements, as a substitute of lanthanum, have a significant effect on phase structure of alloys, elements of cerium and neodymium are beneficial to the formation of Gd_2Co_7-type phase with a space group P 6_3 / mmc. Rare earth elements can decrease the unit cell volume of main phase of alloys, and increase the axis ratio. The results of electrochemical experiment showed that the discharge capacity of alloy electrodes ranged from 342.97 to 380.68 mAh · g -1, and elements of cerium Compared to the electrode of La_2MgNi_9 alloy, the substitution of lanthanum by rare ear th elements did not improve the cyclic stability of alloy electrodes due to the anisotropic structure change of unit cell. While rare-earth elements can to improve the high rate discharge alloy of alloy electrodes, the high rate dischargeability of alloy electrodes could reach the maximum when the unit cell volume of PuNi_3-type structure was about 0532 nm.