The fabrication of high-performance and stable electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of importance for sustainable water-splitting technologies. Herein, the cobalt (Co) nanoparticles and molybdenum carbide (Mo2C) heterostructures anchored N doped carbon (Co/Mo2C@NC-800) was designed as bifunctional electrocatalyst for overall water splitting via a simple pyrolysis approach for metal organic frameworks (MOFs) precursor. This composite shows a remarkable performance for HER and OER with a small overpotential of 121 mV and 311 mV at 10 mA cm(2), respectively. When the optimized electrocatalyst was employed as both anode and cathode for overall water splitting in a two-electrode system, the electrolyzer achieves a low cell voltage of 1.67 V at 10 mA cm(-2) in 1 M KOH, as well as a superior and stable long-time operation of 30 h. The promising hybrid material demonstrates excellent electrocatalysis performance due to effective combination of the best of both worlds: Mo2C with remarkable HER performance and Co nanoparticles with excellent OER activity. The Mo2C possesses strong hydrogen binding energy and Co exhibits prominent electrical conductivity, thus the construction of heterostructures achieves more active sites with different functions and significantly boosts HER and OER process. The novel and effective synthesis strategy provides new insights into the design of outstanding non-noble metal bifunctional electrocatalysts for overall water splitting. (c) 2020 Elsevier Inc. All rights reserved.