Platinum foil electrodes coated with a conducting polymer were used as working electrodes to deposit a second conducting polymer layer by electrolysis. Polyaniline/poly(N-vinylcarbazole), polypyrrole/poly(N-vinylcarbazole) and polypyrrole/polyaniline (or reverse order) films were synthesized on platinum foil electrodes by sequential electrolysis. These films were characterized by confocal Raman microprobe spectroscopy of both the solution and electrode sides of the films.Depending upon conditions, either the second polymer was incorporated into the initially coated layer or a double-layer film was formed with a well-defined interface. Electrolysis of pyrrole and aniline monomer mixtures having molar ratios of pyrrole:aniline greater than 0.12 gave films rich in pyrrole. Polymerization of N-vinylcarbazole and pyrrole monomer mixtures, however, yielded only polypyrrole over a wide range of molar ratios.