Palladium nanoparticles (PdNPs) were synthesized on Platinum (Pt) electrode by employing a potentiostatic pulse method of electrodeposition. The mechanism of electrocrystallization of PdNPs on Pt was investigated in the system containing 1 mM K2PdCl4 in 0.1 M H2SO4. Experimental results show that Pd electrodeposition follows the so-called Volmer-Weber growth mechanism. The electrodeposited PdNPs were characterized by X-ray photoelectron spectroscopy (XPS) and Field emmisision scanning electron microscopy (FESEM). The results obtained suggested the presence of chemisorbed oxygen on the surface of PdNPs. The influence of time of deposition on the size and monodispersity of the deposited PdNPs was investigated. The studies revealed that, the size of PdNPs increased with increase in the time of deposition. The synthesized Pd nanoparticles modified Pt electrode displayed significantly different voltammetric behavior compared to bare Pt electrode and also showed high catalytic activity towards the electrooxidation of formic acid and methanol. To the best of our knowledge, this is the first report of electrosynthesis of Pd nanoparticles using potentiostatic pulse method without using any stabilizing agent or template. (C) 2013 Elsevier Ltd. All rights reserved.