Air- and water-stable, pi-conjugated [-donor-acceptor-](n) oligomers containing thiophene fragments as donors and 9,10-dimesity1-9,10-dihydro-9,10-diboraanthracene (DBA(Mes)(2)) as acceptor units were prepared through Stille-type C-C-coupling protocols. The reaction between 2,6-dibromo-DBA(Mes)(2) (1), 2,7-dibromo-DBA(Mes)(2) (2), 2-bromo-6,7-dimethyl-DBA(Mes)(2) (3), and 2,5-bis(trimethylstannyl)thiophene (7) furnished monodisperse, short-chain model systeins 8(0) (2 x DBA(Mes)(2), 1 x 2,5-thienylene) and 8(1) (3 x DBA(Mes)(2), 2 x 2,5-thienylene) after GPC separation. In the absence of 3, the oligomerization of 1/2 with 7 provided analogous longer chain macromolecules 9 (MALDI-MS reveals up to 7 repeating units; GPC indicates also significantly longer chains). UV/vis absorption spectroscopy suggests that the obtained chain lengths of 9 are already sufficient to reach the maximum effective conjugation length (the lower limit of the HOMO-LUMO band gap corresponds to 2.3 eV). 9 gives rise to a dark orange fluorescence, both in C6H6 solution (phi(f) = 47%) and as thin film (phi(f) = 13%).