The electrochemical bandgaps for different soluble substituted polythiophenes have been measured by cyclic voltammetry. The effect of substituents on the oxidation/reduction potentials is discussed. Bandgaps obtained by cyclic voltammetry have been found to be in general higher than optical bandgaps. Among regioregular polymers substituted with a phenyl group at position 3 of the thiophene ring, examples are found that give very symmetric voltammograms. Rationalization for this behaviour is discussed from a conformational point of view.