The rational design and regulate structure and composition are pivotal for the development of highly efficient oxygen evolution reaction (OER) catalysts for water splitting. In this study, amorphous CoFeP/NC hybrid electrocatalyst has been synthesized by a simple and effective phosphorization of a CoFe-based coordination polymer under N-2 atmosphere. The synergistic effects between the CoFeP and N-doped carbon has led to high electronic conductivity attributed to the optimal Fe contents with N-doped carbon and enlarged electrocatalytic active surface area aroused by the nanostructure of CoFeP/NC, as well as the surface structural evolution of oxyhydroxide/phosphate during OER process. The resulting Co0.35Fe0.17P0.48/NC electrocatalyst can attain a current density of 10 mA/cm(2) at an overpotential of 275 mV with a Tafel slope of 31 mV/dec on glassy carbon electrode and 228 mV on Ni foam electrode in 1 M KOH solution, long-term OER stability of this Co0.35Fe0.17P0.48/NC under the applied potential of 1.53 V vs. RHE demonstrates no obvious decline in current densities of 110 mA/cm(2) within 17 h, which outperforms those of the contrast electrocatalysts in this work and also comparable to that of many of the reported electrocatalysts in the literatures. This Co0.35Fe0.17P0.48/NC electrocatalyst highlights the rational modulation of optimal composition and electronic structure with homogeneous incorporation of the foreign metal-doped and N-doped carbon for the synthesis of highly efficient electrocatalysts toward to the water oxidation reactions. (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.