The La-Mg-Ni-based A2B7-type La0.8Mg0.2Ni3.3Co0.2Six(x=0-0.2) electrode alloys were prepared by casting and annealing. The influences of the additional silicon and the annealing treatment on the structure and electrochemical performances of the alloys were investigated systemically. Both of the analyses of XRD and SEM reveal that the as-cast and annealed alloys are of a multiphase structure, involving two main phases (La, Mg)2Ni7 and LaNi5 as well as one minor phase LaNi3. The addition of Si and annealing treatment bring on an evident change in the phase abundances and cell parameters of (La, Mg)2Ni7 and LaNi5 phase for the alloy without altering its phase structure. The phase abundances decrease from 74.3% (x=0) to 57.8% (x=0.2) for the (La, Mg)2Ni7 phase, and those of LaNi5 phase increase from 20.2% (x=0) to 37.3% (x=0.2). As for the electrochemical measurements, adding Si and performing annealing treatment have engendered obvious impacts. The cycle stability of the alloys is improved dramatically, being enhanced from 80.3% to 93.7% for the as-annealed (950 °C) alloys with Si content increasing from 0 to 0.2. However, the discharge capacity is reduced by adding Si, from 399.4 to 345.3 mA·h/g as the Si content increases from 0 to 0.2. Furthermore, such addition makes the electrochemical kinetic properties of the alloy electrodes first increase and then decrease. Also, it is found that the overall electrochemical properties of the alloys first augment and then fall with the annealing temperature rising.