Electrochemical studies of LiB compound were carried out for its application as anode for lithium-ion battery. The compound exhibited a reversible discharge–charge behavior between 0 and 0.75V versus Li/Li+ with a first discharge capacity of 293mAhg−1. Discharging to 1.0V, the first discharge capacity of LiB compound was 660mAhg−1, but a part of this capacity was irreversible. Impedance spectra were measured at several potentials corresponding to different discharge plateaus. The impedance spectra obtained below and above 0.8V presented significantly different features. The solid electrolyte interphase layer (SEI) was formed below 0.8V and assumed a good performance of LiB electrode in this potential range. The SEI was found to deteriorate above 0.8V, which might be associated with the irreversible discharge capacity.