Raman spectra of polythiophene films electrochemically deposited onto silver and platinum electrodes have been investigated using 514.5 nm laser excitation. Contrary to the case for platinum, the use of roughened silver electrodes leads to the observation of surface-enhanced Raman scattering (SERS), allowing the vibrational characterization of polythiophene in a doped state. Since these vibrational modes are very different from those obtained for the undoped species, this provides a means of evaluating the amount of defects in both states of polythiophene films. According to SERS selection rules, the polythiophene appears to be bound to the silver surface with the ring planes perpendicular to that surface.