A2B7-type electrode alloys with a nominal composition of La0.75-xZrxMg0.25Ni3.2Co0.2Al0.1 (x = 0, 0.05, 0.1, 0.15, 0.2) were prepared by casting and melt-spinning. The influences of the substitution of Zr for La on the structures as well as the electrochemical performances of the alloys were investigated. The results obtained by XRD, SEM and TEM show that the as-cast and spun alloys have a multiphase structure, consisting of two main phases (La,Mg)Ni3 and LaNi5 as well as a residual phase LaNi2. The substitution of Zr for La leads to an obvious increase of the LaNi5 phase in the alloys, and it also helps the formation of a like amorphous structure in the as-spun alloy. The results of the electrochemical measurements indicate that the substitution of Zr for La obviously decreases the discharge capacity of the as-cast and spun alloys, but significantly improves their cycle stability. With increasing the spinning rate, the discharge capacity of the alloys (x≤0.1) first increases and then decreases, while the cycle stability monotonously rises.