A sonogel–carbon–polythiophene microstructured electrode has been synthesised via sonocatalytic procedure. The composite material was characterised by cyclic voltammetry, atomic force microscopy and optical microscopy. A comparison with a similar polythiophene directly cast on a platinum electrode has been made. In contrast with the degrading behaviour (overoxidation) observed at sufficiently positive potentials for alkylsulphanyl substituted polythiophenes cast on the electrode surface, the entrapment of the polymer inside a composite material drastically enhances the stability of the redox-active phase towards irreversible oxidation. In addition, the sonogel–carbon–polythiophene composite represents a good approach to test and, possibly, exploit the electrochemical properties of the polymer which, due to its complete insolubility in the common organic solvents, cannot be adequately cast on an electrode surface or electrosynthesised.