Two pairs of beta,beta'-didodecyl substituted quinquethiophenes linked via a tri- (3) and tetramethylene spacer (4) at their alpha-positions have been synthesized and their electrochemical behavior investigated with cyclic voltammetry in solution and in solid films. Both compounds can be charged to a tetracation in two two-electron transfer steps, which are reversible at room temperature but become partially irreversible at low temperatures. Concentration and scan rate dependent measurements support an intramolecular coupling of the oligothiophene units preferentially next to their bridging site with sigma-bond formation. In solution no electropolymerization can be observed. In the solid state upon oxidation intermolecular coupling of the oligothiophene segments takes place. Conductance measurements confirm the voltammetric findings. Obviously, the mechanism of conductance is based on hopping processes within mixed valence states. (C) 2011 Elsevier Ltd. All rights reserved.