Iron is a key element in the development of Co-free AB5-type hydrogen storage alloys. The aim of this work is to systematically investigate the effects of Fe and Co on the electrochemical properties of LaNi4.6−x Mn0.4M x (M=Fe or Co, x =0, 0.25, 0.5 and 0.75) hydrogen storage alloys under relatively low temperatures (273, 253 and 233K). The results showed that substitution of Fe for Ni reduced the low temperature electrochemical performance much more seriously than that of Co. Exchange current density (I 0), charge-transfer resistance (R ct) and hydrogen diffusion coefficient (D) were determined based on the study of linear polarization, electrochemical impedance spectrum (EIS) and galvanostatic discharge, respectively. Both the hydrogen diffusion in the bulk of alloy particles and the electrochemical reaction at the alloy electrolyte interface were found to be greatly limited as the decrease of temperature. During the EIS analysis, interestingly, we found that the semicircle in the high frequency region increased dramatically with the decrease of temperature. The electrochemical process corresponding to this semicircle was proposed to be related to the oxide layer on the surface of alloy particles. Novel explanations of EIS response in metal hydride electrodes were proposed accordingly.