The A2B7-type lanthanum (La)–magnesium (Mg)–nickel (Ni)-based alloy with single (La,Mg)2Ni7 phase and different amounts of (La,Mg)5Ni19 minor phase was obtained by step-wise sintering. The impact of (La,Mg)5Ni19 phase on the alloy's microstructure and electrochemical performance was subsequently studied. It was found that the average subunit volume in (La,Mg)5Ni19 phase is smaller than that in (La,Mg)2Ni7 phase, resulting in increases of strains inside the alloys and decreases of cell volumes. During battery charge/discharge, the (La,Mg)5Ni19 phase network scattered in the alloys relieves internal stress, alleviates pulverization and oxidation of the alloys, stabilizes the stacking structures against amorphization, and finally improves the cycling stability of the alloys. Furthermore, (La,Mg)5Ni19 phase with higher Ni content desorbs hydrogen ahead of (La,Mg)2Ni7 phase. The reduced hydrogen pressure in (La,Mg)5Ni19 phase can subsequently lead to the fast discharge of (La,Mg)2Ni7 phase, thus making a remarkable improvement in high rate dischargeability at 1500 mA g−1 from 46.2% to 58.9% with increasing (La,Mg)5Ni19 phase abundance from 0 to 37.4 wt.%. Therefore, it is believed that A2B7-type La–Mg–Ni-based alloys with A5B19-type minor phase are promising prototypes for high-power and long-lifetime nickel/metal hydride battery electrode materials.