Low Co AB5-type MmNi3.8Co0.4Mn0.6Al0.2B x (x=0, 0.1, 0.2, 0.3, 0.4) hydrogen storage alloys were prepared by cast and rapid quenching. The microstructures and electrochemical performances of the as-cast and quenched alloys were analysed and measured. The effects of boron additive and rapid quenching technique on the microstructures and electrochemical properties of as-cast and quenched alloys were investigated comprehensively. The experimental results showed that the microstructure of as-cast MmNi3.8Co0.4Mn0.6Al0.2B x (x=0, 0.1, 0.2, 0.3, 0.4) alloys was composed of CaCu5-type main phase and a small amount of CeCo4B-type secondary phase. The abundance of the secondary phase increases with the increase of boron context x. The rapid quenching techniques were used in the preparation of the alloys. The amount of secondary phase in the alloys decreased with the increase of quenching rate. Rapid quenching made lattice constants increase slightly. The effects of rapid quenching on the electrochemical performances of the alloys are very significant. The discharge capacity of the alloys decreased obviously and the cycle stability increased dramatically with the increase of quenching rate. Rapid quenching made the activation capability of the alloys lowered. However, the activate performance and high rate discharge capability as well as discharge voltage characteristic of the alloys were modified obviously with the increase of boron content x.