In this work, a fast, simple, low cost, atmospheric pressure based vapor phase polymerization (VPP) of 3, 4-ethylenedioxythiophene (EDOT) has been utilized with controlled substrate temperature. This technique enabled the production of highly electrically conducting thin films of poly (3, 4-ethylenedioxythiophene) (PEDOT). Well-ordered PEDOT films were produced at a nanometer scale by using layer-by-layer technique. Films showed conductance up to 3208 S/cm, and sheet resistance, 20.55 Ω/□ that is close to commercially available indium tin oxide (ITO) coated glasses. FTIR, Raman, and UV–vis studies revealed a polymer in highly conducting form obtained by controlling the VPP method parameters. The surface morphology was studied by atomic force microscopy (AFM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) measurements were carried out on PEDOT films without any current collector. The VPP PEDOT films have potential to be used in a variety of transparent electrode applications as well as in supercapacitors.