The synthesis of a hybrid material obtained by electropolymerization of a solution of pyrrole and [NEt4](2)[Pd(dmit)(2)] (1,3-dithiole-2-thione-4,5-dithiolate, [dmit](2-), [C3S5](2-)) in acetonitrile solution is reported. FTIR and UV-vis spectroscopy showed that the [Pd(dmit)(2)](2-) anion had been inserted in the polypyrrole framework without modification during the electropolymerization process. Cyclic voltammetry showed that the material has electroactivity undergoing redox processes related to the conducting polymer and the counteranion. The electrochemical results also suggest that the counteranion is not trapped in the PPy matrix undergoing anion exchange during the redox cycle of PPy. The PPy/[Pd(dmit)(2)](2) exhibits good thermal stability and has a higher intrinsic conductivity value (4.27 x 10(-3) S cm(-1)) than do other PPy/dmit films previously studied. (c) 2006 Elsevier Ltd. All rights reserved.