The vapor-phase polymerization (VPP) of poly(3-hexylthiophene) (P3HT) was achieved successfully as an alternative method to conventional solution-based thin film fabrication. Using Fe(III)Cl(3).6H(2)O, a spontaneous reaction of 3-hexylthiophene monomers resulted in the rapid formation of conducting P3HT thin films directly on substrates, such as glass, indium-tin-oxide, and poly(ethylene terephthalate), at thicknesses ranging from 50 to 1000 nm. The VPP of P3HT was achieved using ferric chloride hexahydrate and a 1:1 ratio of a methanol/ethanol mixture as the solvent system. The developed VPP technique can provide good processing consistency with an electrical conductivity, a transmittance, and a surface roughness of approximately 10(-2) S/cm, >90%, and <10 nm, respectively.