The chemical polymerization of pyrrole was studied with the aim of defining the best operating conditions for obtaining conductive fabrics of synthetic fibers. Ammonium persulfate was chosen as the oxidant, and various dopants were tested. Among these, naphtalene-2,6-disulfonic acid disodium salt enabled the lowest surface resistivity to be reached. Hence, several kinetic runs were performed to explain the influence of some operating conditions as oxidant concentration and temperature. A pseudo-first-order kinetic equation was derived, and the reaction rates were found to be practically unaffected by the presence of the textile substrate. Pyrrole polymerization was faster than adsorption of the monomer, suggesting the hypothesis of fast polymerization outside the fibers followed by adsorption onto the fiber surface. The surface coating of polypyrrole was evidenced by microscopic observation of the fiber cross sections. 2006 Wiley Periodicals, Inc.