Tuning the metal-support interaction in electrocatalysts has been proposed as a viable method for manipulating the electronic structure and catalytic activity. In this work, inspired by natural hydrogenase enzyme, electrocatalysts with a hybrid metal-matrix complex using polydopamine (PDA) as a supporting matrix were synthesized for efficient green hydrogen production. Among the various Metal-PDA electrocatalysts, Cu-PDA shows outstanding catalytic activity (low overpotential (ƞ) of 104 mV at 10 mA cm−2 and small Tafel slope of 60.67 mV dec-1) with high stability at neutral pH. Also, the electrochemical impedance spectroscopy analysis verified the fast charge transfer properties of Cu-PDA (2.8 Ω cm2) than PDA (26 Ω cm2), indicating a faster proton-coupled electron transfer process in Cu-PDA electrocatalyst. Therefore, emerging nature inspired organic ligand-transition metal ion complexes can be extensively encouraged as a prospective HER electrocatalyst under neutral conditions.