Metastable single phase with CaCu5 type structure for Co free over-stoichiometric La(NiMn)6 alloys were obtained by non-equilibrium processing of melt spinning. The crystal structure and electrochemical properties were investigated comparatively. The XRD results show that the La(NiMn)6 alloys prepared by melt spinning, in comparison with the as-cast alloys, present a single phase with CaCu5 type. The crystal lattice constants a and c exhibit a anisotropic change. With the increase of cooling rate, the a axis decreases and c axis and ratio of c/a value increase. The electrochemical analyses show that when cooling rate increases from 20 m/s to 50 m/s, the MH electrodes discharge capacity reach 277 mAh/g~256 mAh/g and the capacity retention is 63%~97.8% after 100 cycling number. The alloys prepared by melt spinning show a good cycling stability, but a lower discharge capacity and worse activation kinetics than that of the as-cast alloys.