In this work, isolated fine silver nanoparticles and polypyrrole/silver nanocomposites with diameters of about 10nm on gold substrates were first prepared by electrochemical methods. First, an Ag substrate was cycled in a deoxygenated aqueous solution containing 0.1M HCl from −0.30 to +0.30V versus Ag/AgCl at 5mV/s with 30 scans. Subsequently the Ag working electrode was immediately replaced by an Au electrode and a cathodic overpotential of 0.2V was applied under controlled sonication to synthesize Ag nanoparticles on the Au electrode. Then pyrrole monomers were encouragingly found to be polymerized on the deposited Ag nanoparticles. This polymerization is distinguishable from the known chemical or electrochemical one, due to the electrochemical activity of unreduced species of Ag n + clusters inside the nanoparticles. Also, this polymerization may be ascribed to the oxidizing agent of AuCl4 −, which is present on the Au electrode.