A series of novel Co–S–B systems were prepared by simple chemical reduction method as the anode material for secondary alkaline batteries. The prepared samples were investigated by inductivity coupled plasma optical emission spectrum (ICP), Brunauer–Emmetr–Teller (BET) method, scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray energy dispersive spectroscopy (EDS) and charge–discharge method. It was found that the BET surface area of Co–S–B system increases and its particle size decreases with increasing the sulfur content. Sulfur incorporation suppresses initial capacity fading of Co–B compound due to irreversible dissolution of boron, and Co–S–B electrodes show enhanced electrochemical capacity and excellent cycle performance. The discharge capacity of Co75.4B17S7.6 reaches 513.6mAh/g at a moderate current density of 100mA/g and 470mAh/g after 60 cycles, which is about 1.5 times that of conventional AB5-type alloy. A proper mechanism was proposed to explain the electrochemical reaction process of Co–S–B electrode.