The influence of Cu(OH)2 addition in 7mol/L KOH alkaline electrolyte on the electrochemical properties of La0.75Mg0.25Ni3.5 hydrogen storage alloy electrode was investigated in the testing temperature range of from 25°C to −40°C in this paper. XRD Rietveld analyses shows that the La0.75Mg0.25Ni3.5 hydrogen storage alloy consists of LaNi5 phase, (La, Mg)2Ni7 phase and (La,Mg)Ni3 phase. The maximum discharge capacity and the high-rate dischargeability (HRD) of the La0.75 Mg0.25Ni3.5 alloy electrode both decrease with decreasing testing temperature, which mainly due to the slower hydrogen transfer in the bulk of the alloy and the lower electrocatalytic activity at lower temperatures. The scanning electron microscopy (SEM)/energy dispersive X-ray spectroscopy (EDS) analyses indicate that, with the addition of Cu(OH)2 to the KOH alkaline electrolyte, fine particles of metal Cu can be coated on the La0.75Mg0.25Ni3.5 alloy electrode surface during charging process by electrodeposition. The Cu powders deposited on the La0.75Mg0.25Ni3.5 alloy electrode can improve the alloy’s low-temperature discharge properties by decreasing its charge-transfer resistance and increasing its exchange current density. The cyclic stability of the Cu-deposited La0.75Mg0.25Ni3.5 alloy electrode can be also improved to a certain extent by increasing its corrosive resistance in KOH alkaline electrolyte.