In this work, the characteristics of polypyrrole (PPy) films electrode posited onto an electrochemically roughened gold substrate with bimetallic silver and gold nanoparticles were first investigated. First, a silver substrate was roughened by a triangular-wave oxidation-reduction cycle (ORC) in an aqueous solution containing 0.1 M HCI. Subsequently, a gold substrate was roughened by a similar ORC treatment in this used solution. The results revealed that the surface of the roughened gold substrate demonstrated two different kinds of deposition domains because of the modification of silver nanoparticles. Encouragingly, some novel characteristics of PPy deposited onto this substrate were observed, in comparison with those on the roughened gold substrate without the modification of silver nanoparticles. They included a denser and more compact surface morphology, higher oxidation degree, increased conductivity, and improved surface-enhanced Raman scattering. Furthermore, the nucleation and growth mechanism for PPy electropolymerization on this silver-modified roughened gold substrate was distinguishable from that on the unmodified one. (c) 2006 Wiley Periodicals, Inc.