A numerical and experimental study of the plasma variables in the synthesis of polyaniline in radio-frequency (RF) glow discharges is presented. The plasma variables were measured on the basis of data collected by electrostatic Langmuir probes placed along the reactor. The results showed the distribution of the electric potential and the electronic energy and density during the polymerization reactions. The region with the lowest energy was the zone adjoining the grounded electrode, whereas the maximum energy was located near the RF electrode. In the second zone, the energy was around twice that of the grounded zone, and both were beyond the typical atomic bonding energy found in most organic polymers. (C) 2003 Wiley Periodicals, Inc.