The reduced pressure synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) with sheet-like morphology has been achieved with the introduction of an amphiphilic triblock copolymer into the oxidant thin film. Addition of the copolymer not only results in an oxidant thin film which remains liquid-like under reduced pressure but also induces structured growth during film formation. PEDOT films were polymerized using the vacuum vapor phase polymerization (VPP) technique, in which we show that maintaining a liquid-like state for the oxidant is essential. The resulting conductivity is equivalent to commercially available indium tin oxide (ITO) with concomitant optical transmission values. PEDOT films can be produced with a variety of thicknesses across a range of substrate materials from plastics to metals to ceramics, with sheet resistances down to 45 Omega/square (ca. 3400 S.cm(-1)), and transparency in the visible spectrum of >80% at 65 nm thickness. This compares favorably to ITO and its currently touted replacements.