Surface modification is a promising approach to modulate the electrocatalyst properties for their further use in energy storage and conversion. In this work, electrochemical-based approach was proposed to generate metallic particles-supported graphite rod (GR). The approach is based on the cathodic activation of GR in the presence of alkali metal salts in dry organic solvent. The activated GR possess a high reducing power that was successfully employed to spontaneously reduce metallic salts in aqueous media. The surface analyses confirm the formation of metallic nanoparticles supported GR. Interestingly, the metallic nanoparticles were found to be generated onto and intercalated into the GR. Next, the generated materials were used as electrocatalyst to drive the hydrogen evolution reaction. Our results demonstrate that the electrocatalytic performances depend on various parameters including the radius of the alkali metal cation and the injected charge during the electrochemical activation. The as-prepared Pt/Li-GR exhibits the best electrochemical activity and stability toward the hydrogen evolution reaction. The necessary overpotential value to reach a current density of 10 mA cm−2 is 40 mV for the Pt/Li-GR, and almost negligible overpotential change is observed during the stability tests. In addition, the proposed approach was successfully used to generate Pd/Li-GR catalyst. More impressively, the latter displays higher HER performances when compared to other reported Pd-based catalysts and comparable performance with commercial Pt/C catalyst.