In this review, we provide a comprehensive overview of the MoS₂ nanomaterials, summarizing recent related studies on structures, properties, synthesis techniques and recent progress on hydrogen evolution reaction (HER). Base on its crystalline anisotropy arising from the sandwiched structure of S–Mo–S layers, four poly-types of MoS₂ structures have been identified, viz. 1T MoS₂, 1H MoS₂, 2H MoS₂ and 3R MoS₂. After their structures investigated, we summarized its diverse properties, such as activity, friction, catalytic, optical and electronic properties. Next, we describe the general synthetic approaches, viz. physical and chemical methods, also address future directions for various practical applications of novel MoS₂-based materials. Some key recent progress on HER are addressed, which are substantiated by examples from the existing literature and some new results. Finally, suggestions for future MoS₂ based catalyst designs for HER are given.