In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M=Cu, Al, Mn). A new La-Mg-Ni system electrode alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M=Cu, Al, Mn; x=0, 0.1) were prepared by casting and rapid quenching. The effects of element substitution and rapid quenching on the microstructures and electrochemical performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys have a multiphase structure, including the (La, Mg)Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. The rapid quenching significantly improves the composition homogeneity of the alloys and markedly decreases the grain size of the alloys. The Cu substitution promotes the formation of an amorphous phase in the as-quenched alloy, and a reversal result by the Al substitution. The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, whereas it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al>Cu>Mn, and negative influence on the discharge capacity is in sequence Al>Mn>Cu. The rapid quenching significantly enhances the cycle stability of the alloys, but it leads to a different extent decrease of the discharge capacity of the alloys. In order to improve the electrochemical cycle stability of La-Mg-Ni system (PuNi3-type) hydrogen storage alloy, Ni in the alloys was partially substituted by M (M = Cu, Al, Mn) The effects of element substitution and rapid quenching on the microstructures and electrochemical (Electrode system alloys La0.7Mg0.3Ni2.55-xCo0.45Mx (M = Cu, Al, Mn; x = 0, 0.1) were prepared by casting and rapid quenching performances of the alloys were investigated. The results by XRD, SEM and TEM show that the alloys have a multiphase structure, including the (La, Mg) Ni3 phase, the LaNi5 phase and the LaNi2 phase. The rapid quenching and element substitution have an imperceptible influence on the phase compositions of the alloys, but both change the phase abundance of the alloys. the rapid quenching significant improves the composition homogeneity of the alloys and markedly reduce the grain size of the alloys. phase in the as-quenched The electrochemical measurement indicates that the element substitution decreases the discharge capacity of the alloys, yet it obviously improves the cycle stability of the alloys. The positive influence of element substitution on the cycle life of the alloys is in sequence Al> Cu> Mn, and negative influence on the discharge capacity is in sequence Al> Mn> Cu. The rapid quenching significantly enhance the cycle stability of the alloys, but it leads to a different extent decrease of the discharge capacity of the alloys.