Polymer–clay nanocomposites based on poly(3,4-ethylenedioxythiophene) (PEDOT) and montmorillonite were synthesized and characterized. Three different syntheses have been explored: (i) intercalation of 3,4-ethylenedioxythiophene (EDOT) and in situpolymerization, (ii) clay expansion and in situ oxidative polymerization of EDOT, and (iii) direct intercalation of PEDOT from an aqueous dispersion of it doped with polystyrene sulfonate (PEDOT–PSS). The nanocomposites were characterized by various physicochemical techniques, XRD, FTIR, DTA-TG, CHN elemental analysis and SEM. The electrical behaviour of the resulting materials was analyzed by EIS. The dependence of the electrical properties on synthetic procedures has been evidenced as the materials prepared by method (ii) with intercalated and extra-framework PEDOT were the ones which showed better electrical conductivity.