Abstract Developing a sustainable non-noble hybrid electrocatalyst for effective electrocatalysis is the most crucial task; particularly in sustainable hydrogen energy production in the realm of energy conversion. In this work, effective thermal pyrolysis process followed by phosphorization strategy was employed to prepare and fabricate ZIF-67 (Zeolitic imidazole) assisted Co2P/N doped carbon electrocatalyst for hydrogen evolution reaction (HER). The optimized Co2P/N–C electrocatalyst exhibited hollow porous nanostructures as confirmed from the scanning electron microscopy. The achieved porous nanostructure improved the efficiency of the charge and mass transportation which is confirmed by the BET analysis, has high surface area value of 94.731 m2/g. In addition, a transition metal atom can regulate reactants adsorption and desorption capacity by modulating Co and P electronic configuration. The electrochemical studies of fabricated ZIF-67 derived Co2P/N–C electrode were analyzed using 1.0 M alkaline potassium hydroxide (KOH) medium in 3 electrode system process. Whilst, optimizing the pyrolysis temperature during the phosphorization will remarkably enhance the favourable characteristics of the hydrogen generation. Notably, the optimized ZIF-67 derived Co2P/NC at 350 °C electrode exhibited low overpotential (135 mV) at minimum 10 mA/cm2 and low 120.3 mV/dec Tafel slope. Besides, electrode stability at 10 mA/cm2 current density was verified by chronoamperometry test. Hence, this study furnishes the potential technique for the development of advanced hybrid MOF electrocatalyst as a successful alternative on large scale.