To further explore the π-conjugated systems of anthracene bisimide (ABI) and investigate their electronic properties, we synthesized donor–acceptor linear arrays. These arrays consist of an ABI unit as the acceptor and a 9,10-anthrylene unit as the donor, linked by a butadiynylene spacer. We constructed these donor–acceptor arrays through Hay coupling of the corresponding 9,10-diethynylABI derivative with a 9,10-diethynylanthracene derivative. Theoretical calculations and electronic spectra analysis were employed to compare the photophysical properties of these compounds with those of their acetylene analogs. Moreover, we evaluated the intramolecular electronic interactions between the ABI and anthrylene units, focusing on the effects of the butadiynylene spacer and array sequences.