The La0.5Pr0.2Zr0.1Mg0.2Ni2.75Co0.45Fe0.1Al0.2 (M-1) and Zr0.65Ti0.35(Mn0.2V0.2Cr0.15Ni0.45)(1.76) (M-2) hydrogen storage alloys were prepared by inductive melting. In addition, the M-1+30 wt.% M-2 composites were successively prepared by using high-energy ball milling technology. From the X-ray diffraction (XRD) analysis, it was found that M-1 and M-2 alloys still retained their respective main phases in the M-1+30 wt.% M-2 composites. The scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) indicated that the decrease in discharge capacity of M-1 and M-2 alloy electrodes was ascribed to the oxidation-dissolution of La, Pr, Mg and Ti, Mn, V, Cr active elements, respectively. The electrochemical studies showed that the M-1+30 wt.% M-2 composite electrode ball milling for 5 min exhibited excellence cyclic stability (92.3%) after 80 charge/discharge cycles, which was higher than 77.7% and 85.6% of M-1 and M-2 alloy electrodes, respectively. Moreover, at the discharge current density of 1200 mA/g, the high rate discharge ability (HRD) of the M-1+30 wt.% M-2 composite electrode increased from 61.5% (5 min) to 70.3% (10 min). According to the linear polarization, Tafel polarization and cyclic voltammograms (CV), the electrochemical kinetics of hydrogen reaction on the surface of the electrode and hydrogen diffusion rate in the bulk of alloy were also improved in the M-1+30 wt.% M-2 composite with increasing ball milling time.