There are great challenges to develop and fabricate a high performance, low-cost and stable non-platinum catalyst for hydrogen evolution reaction (HER). In our study, we firstly developed a simple method to successfully fabricate a new MoS2/NiCo2S4 heterostructure by a two-step hydrothermal method, and studied the HER property of MoS2/NiCo2S4, where the as-prepared NiCo-layered double hydroxide (NiCo-LDH) was used as the precursor of NiCo2S4. Benefitting from the prominent synergistic effect between NiCo2S4 and MoS2, MoS2 provided massive catalytic active edge sites, and NiCo2S4 enhanced the conductivity of the composite. As a result, the MoS2/NiCo2S4 showed excellent HER catalytic activity, with a current of 10 mA cm(-2) at overpotential of 94 mV for HER and a low Tafel slope of 46 mV dec(-1), and good cycling stability in Alkaline Media. As well as, our work offered one promising high active and stable non-platinum catalyst for overall water splitting. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.