Electrocatalytic performance of fuel cells is highly dependant on the size, distribution density of nanoparticles and on the availability of adsorption sites for an electrochemical reaction. To replace the commercially expensive Pt/C catalyst from FCs, a new nanomaterial was designed through dual interactions (covalent and π-π stacking interaction) to maximize the adsorption sites for the reduction of O2 via 4e− transfer reaction.The study gives a detailed discussion on the role of AMP (heteroatom) on the rGO surface in obtaining ultra-small PdNPs through several spectroscopic techniques. Oxygen reduction reaction performance of rGO-AMP-Pd was assessed by different NPs size, their distribution density (rGO-Pd), and the availability of nitrogen species (rGO-AMP) as well. The statistical analysis through various electrochemical studies revealed the incompetency of rGO-Pd and rGO-AMP in terms of surface area, onset potential, current density and number of electrons, as compared to Pt/C catalyst. Conversly rGO-AMP-Pd, high population of ultra-small (1 – 3 nm) PdNPs dispersed on the rGO-AMP surface showed enhanced electrocatalytic activity due to comparatively large surface area and availability of abundant active sites for the adsorption of O2. The study shows a facile approach for synthesis of ultra-small PdNPs and cost-friendly catalyst for the replacement of Pt/C catalyst in FCs.