A systematic investigation was carried out by means of cyclic voltammetry, chronoamperometry and chronopotentiometry on 3,6-dimethylthieno[3,2-b]thiophene (DMTT) electropolymerisation on vitreous carbon in acetonitrile (ACN) containing 0.1 M LiClO4. The electrochemical doping-undoping process was reversible and the coulombic efficiency over a charge-discharge cycle was ca. 100%. The electropolymerisation mechanism was unchanged by the presence of methyl groups. When an aluminium electrode was used, poly(DMTT) deposition could only be performed in the potentiostatic mode. In this case, electropolymerisation hindered the pitting process on Al, which was initiated in the early stages of anodisation.