Composite material consisting of poly(3,4-ethylenedioxythiophene) (PEDOT), including Au nanoparticles encapsulated by N-dodecyl-N.N-dimethyl-3-ammonium-1-propanesulphonate(SB12) is synthesised by constant-current method on ITO glass, in aqueous medium, leading to an electrode coating. The synthesis process is followed by UV-vis spectroelectrochemistry, both in normal-beam and in parallel-beam configurations. Under the same experimental conditions PEDOT is also synthesised by electropolymerisation only in the presence of LiClO4 supporting electrolyte, as well in solutions also containing SB12. The data relative to the electrosynthesis of the three materials are compared. The composite material based on the conductive polymer matrix including Au nanoparticles has been characterised by SEM,TEM, ICP, Raman and UV-vis spectroscopies. The behaviour of the three different electrode coatings with respect to p-doping process has been studied by conventional electrochemical techniques and by potentiostatic and potentiodynamic UV-vis spectroelectrochemical methods. Conclusions are drawn out about the effect of the presence of the surfactant and of Au nanoparticles on the electrochemical properties of the electrode system. (c) 2007 Elsevier Ltd. All rights reserved.