We report about development and application of a novel electroless NiCoP alloy coating, developed for the first time by a chemical reduction method, for hydrogen evolution reaction. Incorporation of cobalt into the Nip mass effectively increases the number of active sites during hydrogen evolution reaction. High catalytic activity of the coated electrode is attained due to the tuned content of 25.06 wt% phosphorous and 4.26 wt% cobalt. A low overpotential of -112 mV at a current density of -10 mA cm(-2 )is achieved with the coating during hydrogen evolution reaction in alkaline media. A Tafel slope of 110 mV dec(-1) with a high exchange current density of 24.67 mA cm(-2) is achieved with the coating. A low R(ct )dec(-1) value of 2.7 Ohm and a high C(dl )value of 3.15 mu F of the NiCoP alloy coating is also achieved due to the synergistic effect of Co and Ni with P. A high charge delocalization is achieved by the tuning of Co, Ni and P. Volmer-Heyrovsky mechanism is followed during the hydrogen evolution reaction. The coating is highly stable on the electrode under alkaline condition. The present catalyst has reasonable performance competent to some other coating systems developed recently in this field. The present catalytic coating system exhibits unique performance due to the critical alloy content. The present chemical reduction method to develop the present active coating system is promising in respect of its application for large or irregular shaped electrodes that are actually required for industrial application. (C) 2019 Elsevier Ltd. All rights reserved.