A nanocasting procedure, employing polymeric bicontinuous microemulsions as templates, suitable for the production of a diverse spectrum of nanoporous monolithic materials having three-dimensionally continuous, δ100 nm pores was developed. A nanoporous PE monolith is first derived from a blend containing 42.5% PE, 42.5% PEP, and 15% PE-PEP by volume. Then, the oxidative polymerization of EDOT initiated by iron(III) tris-p-toluenesulfonate is conducted within the PE pore system. PE monolith is added to a large excess of EDOT, inducing spontaneous infiltration through capillary action. After several hours, the monolith is removed, washed with excess isopropanol, and dried under vacuum. Nitrogen sorption measurements were further used to determine the pore characteristics of the PEDOT monoliths. Large, micrometer-sized regions of ITO substrate, completely devoid of any supported film, are observed. These results suggest either poor adhesion of the PEDOT to the substrate or inadequate access of the EDOT infiltrated into the PE template to the film.