Star-shaped complexes of π-conjugated chromophores are currently of great interest for use in optoelectronic devices.1 Recently, different planar central cores involving three thiophene rings fused to a benzenic ring (BTTs) have been described. In these systems, the coplanarity and extended π-conjugation of the BTT skeleton should promote intermolecular π-stacking, which would induce strong aggregation and enhanced packing in the solid state of BTT-containing molecules. We propose here the study of a BTT conjugated system with DPPT fragments, in which three DPP2T units are linked to a central rigid trithienobenzene core. Comparison with homologous linear systems, based on the benzodithiophene (BDT) unit and the naphtodithiophene (NDT) unit,2 will be carried out in order to elucidate the effect of star-shaped configuration versus linear conformation on the optical and electrical properties.