AbstractThe design and synthesis of strained aromatics provide an additional insight into the relationship between structure and properties. In the last years, several approaches to twist pyrene‐fused azaacenes have been developed that allow to introduce twists of different sizes. Herein, we describe the synthesis of a new set of twisted dibenzotetraazahexacenes constituted by fused pyrene and quinoxaline residues that have been distorted by introducing increasingly larger substituents on the quinoxaline residues. Their twisted structure has been demonstrated by single‐crystal X‐ray diffraction. Furthermore, absorption, fluorescence, electrochemical and theoretical studies shine light on the effects of the substituents and twists on the optoelectronic and redox properties.