The reasonable design and construction of non-precious metal electrocatalysts with low cost and high performance is critical for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, a facile polymerization-pyrolysis method is proposed to encapsulate Co2P nanoparticles in co-doped hollow carbon shell by using ZIF-67 and Pcontaining polymers as precursor. The unique construction not only effectively prevents nanoparticles from detaching, showing good stability after long-term testing, but also provides abundant active sites, large surface areas and large pore volumes, enabling the electrolyte and electrode material to full contact. As expected, the Co2P/NPSC-800 performs superior HER performance with low overpotential of 173 mV at 10 mA cm(-2) and excellent stability of 88% retention for 35 h and OER performance with low overpotential of 320 mV at 10 mA cm(-2), which endows Co2P/NPSC-800 with good catalytic activity in overall water-splitting. Furthermore, density functional theory (DFT) calculations reveal that the metallic property and the decreased reaction barriers of Co2P can promote the catalytic reactions. This work offers an effective route in synthesizing other transition metal phosphides with high catalytic properties. (C) 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.