The nonstoichiometric La-rich mischmetal (designated by Ml)-based hydrogen storage alloy with a composition of Ml(Ni0.64Co0.20Mn0.12Al0.04)4.76 was prepared by arc melting and annealed at 1173 K for 10 h to investigate the effect of annealing treatment on the microstructure and electrochemical characteristics of the alloy. X-ray diffraction analysis showed that annealing can cause a release of the crystal lattice strain and an increase in amounts of the La2Ni7-type second phase in Ml(Ni0.64Co0.20Mn0.12Al0.04)4.76 alloy. Scanning electron microscopy and electron probe microanalysis examinations indicated that annealing leads to disappearance of the dendrite structure in the as-cast alloy, growth of crystal grain, and decrease of composition segregation. The annealing at 1173 K for 10 h flattened and extended the potential plateau and inprovement in electrochemical characteristics was discussed based on the alloy microstructure change induced by annealing.