Three-dimensional network of branched fibers of conducting polypyrrole was synthesized by interfacial polymerization method in the presence of sulfonated -cyclodextrin (S CD) as the dopant. A high surface area of open-pore polypyrrole structure was obtained with the aid of S CD, and the incorporation of S CD units into the polypyrrole fibers was confirmed during the interfacial chemical polymerization. The effect of synthesis conditions such as the concentration of S CD in the polymerization media, the type of oxidant, the reaction temperature, and the electrical properties of polypyrrole-S CD was investigated. It was found that the concentration of S CD strongly affects the morphology. The resulting polymer was characterized with SEM, UV-vis spectroscopy, FT-IR, EDAX, and ESCA measurements.