A concise organolithium-free route to build electron-accepting molecules consisting of two 2-(11-oxoanthra[1,2-b]thiophen-6-ylidene)propanedinitrile units connected by functionalized π-conjugated linkers was developed. Annulation of two thiophene rings in one step was achieved through chemoselective cyclocondensation of a bis(ethynylanthraquinone) substrate with sodium sulfide. Finally, electron-accepting dicyanomethylene moieties were introduced by Knoevenagel condensation with malodinitrile. The synthesized 2,2′-[2,2′-arenediylbis(11-oxoanthra[1,2-b]thiophene-6-ylidene)]dipropanedinitriles were studied by UV/Vis and fluorescence spectroscopy, cyclic voltammetry, and DFT calculations. The acceptor properties of these compounds were confirmed by efficient light-induced electron transfer in their blend with a donor polymer, poly(3-hexylthiophene-2,5-diyl), detected by electron paramagnetic resonance spectroscopy.