The suitable hydrogen-binding free energy (Delta G(H*)) of active sites for hydrogen evolution reaction (HER) is the key for enhancing the electrocatalytic performances of transition metal based electrocatalysts. Usually metal/nonmetal elemental doping and unique nanostructure can be used to adjust the M-H bonding energy for accelerating both generation and departure of H-2. Herein, a simple in-situ phos-phorsulfurization method has been used to synthesized nickel cobalt phosphosulphide (NiCoP vertical bar S/CC) nanoneedles grown on the surface of carbon cloth (CC) at low temperature as electrocatalyst for hydrogen evolution reaction (HER) in both acid (0.5 M H2SO4) and alkaline (1.0 M KOH) electrolyte solution. Typically, NiCo2O4/CC with nanoneedles structure is used as precursor. And NaH2PO2 and H2S is used as phosphorus and sulfur source, respectively. Compared with single metal phosphophides, the enhanced electrocatalytic performance of NiCoP vertical bar S/CC for HER can be attributed to the formation of new specie phosphosulphide and synergistic effect between phosphosulphide and carbon support CC. This work provide a new method with adjusting Delta G(H*) of active sites for preparing the excellent electro-catalysts for water splitting. (C) 2018 Elsevier Ltd. All rights reserved.