A new molecular self-assembly process based on the alternate deposition of a p-type-doped electrically conductive polymer and a conjugated or non-conjugated polyanion has been developed. In this process, monolayers of electrically conductive polymers are spontaneously adsorbed on to a substrate from dilute solutions and subsequently built up into multilayer thin films by alternate deposition with a soluble polyanion. To date, we have successfully utilized this technique to assemble thin films of polypyrrole, polyaniline and poly(3-hexylthiophene). Conductivities as high as 40 S cm-1 can be readily obtained on films containing as few as four deposited layers. Since it is a layer-by-layer deposition process, it is also possible to use this approach to fabricate complex multilayer thin films containing layers of different conducting polymers. The ability to readily fabricate multilayer thin films of doped conducting polymers via a molecular self-assembly process opens up completely new vistas with regard to the thin film processing of conducting polymers and related electroactive materials.