How to enhance the catalytic performance of electrocatalyst for the hydrogen evolution reaction (HER) is the main focus among many researches. In this work, an efficient hybrid composed of CoP nanorods (NRs) and N, P co-doped carbon flakes (NPCFs) which were synthesized by direct pyrolysis of the mixture of biomass macromolecule sodium alginate and ammonium hypophosphite was constructed. The assynthesized CoP/NPCFs hybrid catalyst exhibits efficient electrocatalytic activity with a low onset overpotential (45 mV), small Tafel slope (67 mV dec(-1)), high exchange current density (1.37 x 10(-3) mA cm(-2)), large electrochemical double-layer capacitance (9.25 mF cm(-2)) and good stability for HER in 0.5 M H2SO4 solution. The good HER electrocatalytic performance derived from the more defects and active sites in the catalyst as well as the strong synergetic effect between NPCFs and CoP NRs. This study opens a door for designing low-cost transition metal phosphide catalysts decorated heteroatom doped carbon materials for water splitting. (C) 2017 Elsevier Ltd. All rights reserved.