Acenes and N-heteroacenes have been synthesized and studied for over a century because of their fundamentally interesting materials properties and promise for device applications. Within this context, our laboratory has previously synthesized nitrogen-containing tetrabenzo[de,hi,op,st]pentacenes via an aza-Diels–Alder reaction-based approach, and herein, we expand our methodology to obtain substituted, expanded, functionalized, and dimeric tetrabenzoacenes. Overall, our study adds to the limited number of tetrabenzoacene derivatives reported to date and may open further opportunities for these materials in organic optoelectronics applications.