To reduce the reaction time, electrical energy consumption, and cost, binary α-NiS–β-NiS has been synthesized by a rapid, one-pot, hydrothermal autoclave microwave method within 15min at temperatures of 160–180°C. The microstructure and morphology of the α-NiS–β-NiS products were characterized by means of X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). At 140°C, pure hexagonal NiAs-type α-NiS phase was identified from the XRD patterns. With increasing reaction temperature (160–180°C), the XRD evidence indicates that an increasing fraction of rhombohedral millerite-like β-NiS is formed as a secondary phase. The α-NiS–β-NiS sample synthesized at 160°C yielded good electrochemical performance in term of high reversible capacity (320mAhg−1 at 0.1C up to 100 cycles). Even at high rates, the sample operated at a good fraction of its capacity. The likely contributing factor to the superior electrochemical performance of the α-NiS–β-NiS sample could be related to the improved morphology. TEM imaging confirmed that needle-like protrusions connect the clusters of α-NiS particles, and the individual protrusions indicated a very high surface area including folded sheet morphology, which helps to dissipate the surface accumulation of Li+ ions and facilitate rapid mobility. These factors help to enhance the amount of lithium intercalated within the material.