A new strategy to obtain distorted pyrene-fused azaacenes is reported. The careful alignment and selection of substituents give rise to highly twisted pyrene-fused azaacenes. A combined global and local theoretical analysis shows how the strain is generated and dispersed across the aromatic backbone. Furthermore, simulation of the observed optoelectronic properties shines light on the structural factors that govern the properties of twisted pyrene-fused azaacenes.