Due to the rapid development of alkaline polymer electrolyte fuel cells and water splitting, it is becoming increasingly urgent to develop non-precious metal electrocatalysts for the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) in alkaline medium. Herein, Co2P/CoP hybrid is synthesized from cobalt carbonate hydroxide (CoCH) precursor, and further evaluated for the electrocatalytic HOR and HER in alkaline electrolytes. Specifically, benefiting from the reasonable hybrid structure that integrate suitable hydrogen adsorption energy of CoP and excellent conductivity of Co2P, Co2P/CoP hybrid exhibits excellent catalytic activities. The Co2P/CoP@NF hybrid has impressive HER activity, with a cur-rent density of -10 mA cm(-2) at the overpotentials of -61 mV and the Tafel slope of 55.1 mV dec(-1), which can compete with recently reported transition metal phosphides and cobalt-based catalysts. In addition, the exchange current density of Co2P/CoP@NF hybrid is -0.82 mA cm(-2) for HOR, which is close to commercial Pt/C catalyst (similar to 1.14 mA cm(-2)). (C) 2020 Elsevier Inc. All rights reserved.