wileyonlinelibrary.comHence, developing effi cient and economical electrocatalysts for overall water splitting is one of the main challenges of current research. [7][8][9] Recently, there have been important fi ndings regarding (i) the use of amorphous molybdenum sulfi de (a-MoS x ) catalysts for HER [10][11][12][13][14] which exhibits signifi cantly higher HER electrocatalytic activity than its crystalline molybdenum disulfi de [ 15 ] and (ii) the use of Co-based layered double hydroxide for OER due to the formation of catalytic active Co species layer on the surface when driven by electrical energy, [16][17][18][19][20] and (iii) the ability of its layered structure to facilitate the diffusion and proton-coupled electron transfer of electrolytes. [ 21 ] However, bifunctional electrocatalysts which are effective for both HER and OER in the same electrolyte environment remain underdeveloped. Such bifunctional electrocatalysts can lead to high performance catalytic activity with drastic cost reduction when applied to the alkaline water splitting which is getting the spotlight as a strong candidate for commercializing large-scale production of hydrogen and oxygen. [22][23][24][25][26][27] Here we demonstrate that the hybrid containing cobalt and molybdenum is a highly active and stable catalyst for both HER and OER in alkaline media. In particular, the HER catalytic activity shows an overpotential of 143 mV at a current density of 10 mA cm −2 for mass loading of 0.2 mg cm −2 (as compared with an overpotential of 70 mV by 20% Pt/C) and the OER catalytic activity shows an overpotential of 380 mV at a current density of 10 mA cm −2 for mass loading of 0.2 mg cm −2 (as compared with overpotential of 325 mV by IrO 2 ). Furthermore, in a two-electrode system of the catalyst, an overpotential of only 1.58 V was required for overall water splitting at a current density of 10 mA cm −2 as well as durability at 1.6-1.8 V during 100 000 s. This performance makes the CoS Co(OH) 2 @aMoS 2+ x /NF hybrid catalyst as one of the best overall water splitting catalysts. The origins of specialized active species for HER and OER are probed.Developing effi cient and economical electrocatalysts for hydrogen evolution reaction and oxygen evolution reaction with readily available metals is one of the main challenges for large scale hydrogen/oxygen production. This study reports one step synthesis of cobalt and molybdenum hybrid materials for high performance overall water splitting. The binder-free CoS-doped β-Co(OH) 2 @ amorphous MoS 2+ x is coated on nickel foam (NF) to form 3D networked nanoplates that have large surface area and high durability for electrochemical reactions. The catalytic activity of electrocatalyst for hydrogen evolution is mainly attributed to the unsaturated sulfur site of amorphous MoS 2+ x . Meanwhile, the CoS-doped β-Co(OH) 2 plays the major role in oxygen evolution. CoS-doped β-Co(OH) 2 and aMoS 2+ x are strongly bound to each other due to CoS x bridging. This CoS Co(OH) 2 @aMoS 2+ x /NF hybrid exhibits excel...