In this work, the microstructure and electrochemical properties of Co-free MlNi4.0Al0.3Si0.1Fe0.6 hydrogen storage electrode alloys prepared by both conventional casting and melt-spinning processes at different solidification rate were studied comparatively. XRD analyses indicated that both as-cast and melt-spun alloys were of the CaCu5-type structure single phase, but the crystallizability and homogeneity of the melt-spun alloys were improved. The optical microscope and EDS analyses showed that the melt-spun alloys had a fine cellular structure and a more homogeneous composition than that of the as-cast alloy which had a coarse dendrite structure with noticeable composition segregation. The electrochemical tests indicated that the melt-spun alloys showed a good activation property and much better cycling stability, but lower discharge capacity and high-rate dischargeability. It is found that the decrease in both exchange current density I0 and the diffusion coefficient D of hydrogen in alloy bulk is the main reason for the degraded HRD of melt-spun alloys. The change of electrochemical properties of the alloy treated by rapid solidification process is related to the microstructure of the alloy.