We report here the synthesis and characterisation of extended conjugated systems consisting in a 2,2′-bi(3,4-ethylenedioxy)thiophene (bi-EDOT) unit end-capped with dithiafulvalenyl groups (1). Crystallographic, optical and electrochemical data show that the combination of the electron-releasing effect of the ethylenedioxy groups with the full self-rigidification of the molecule by intramolecular interactions lead to a new series of extended conjugated systems with ...