Molecular packing and microstructure can play a crucial role in the photophysical and electronic properties of organic semiconductor materials. This article presents six pyrene-fused dibenzoazatetracenes 3 and the relationship between their molecular structures and the emission, and as well as the morphology has been investigated. All of the compounds display an aggregation-caused emission quenching effect due to the extended π-conjugation associated with the close π-π stacking in their crystal structures. In terms of fluorescence, the compounds emitted sky-blue emission with a maximum peak (λ maxem) in the range 469-474 nm with a quantum yield (Φ f) of 0.37-0.50 in solution. In the solid state, the emission maximum red-shifts to~528 nm and possesses a relatively low quantum yield (< 0.16). In addition, the electronic effects of the terminal group shows only a limited effect on the emission behavior. On the other hand, tert-butyl groups have been introduced at the pyrene core, and contribute to enhance the solubility of the compound, and also improve the quality of the morphology.