The water splitting reaction via electrocatalyst is a potential method for hydrogen evolution reaction (HER), and metal free electrocatalytic material with excellent performance are in great demand for future applications. In this context, a novel, facile and efficient route for the synthesis of highly conjugated azomethine functionalized graphitic carbon nitride has been proposed. The graphitic carbon nitride (GCN) functionalized with azomethine moiety by using various proportions GCN‐x%DMAC (x=0.1, 0.5, 1.0, 5.0, 10.0) of p‐dimethyl amino cinnamaldehyde (p‐DMAC) leads to introduction of azomethine moiety onto the GCN matrix did not affect the original framework of GCN network, but it efficiently enlarged its π‐delocalized system, increased its surface area and enhanced the electrocatalytic properties. All the structural and morphological properties of synthesized materials have been analyzed by XRD, FTIR, XPS, BET, HRTEM and FESEM with EDS analysis. Furthermore, the GCN‐5.0% DMAC exhibits superb HER performance with onset potential near to 0 V, and a low overpotential of 18.7 mV at 5 mA cm‐2, and extremely ultrasmall tafel slope (46.8 mV dec‐1) in an 0.5 M H2SO4. This study lays the door for interfacial engineering to be used as an efficient method for economically developing electrocatalysts.This article is protected by copyright. All rights reserved.