AbstractA series of novel acceptor–donor–acceptor triad systems, consisting of head‐to‐tail‐coupled oligo(3‐hexylthiophene)s integrated between two terminal perylenemonoimides are described. These hybrid molecules, which differ by the length of the oligothiophene units from a quaterthiophene up to a dodecithiophene were synthesized by an effective palladium‐catalyzed Ullmann‐type homo‐coupling reaction in good yields. The optical and electrochemical properties of these compounds were determined, and on the basis of this series structure‐property relationships have been established which provide vital information for the fabrication of the corresponding photovoltaic devices. Because the synthesized perylenyl‐oligothiophenes distinguish themselves by a high absorption between 300 and 550 nm and an almost complete fluorescence quenching of the perylene acceptor, they meet the requirements for organic solar cells. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)