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The incorporation of heteroatoms into hydrocarbon compounds greatly expands the chemical space of molecular materials. In this context, B−N doping takes a center stage due to its isosterism with a C=C‐bond. Herein, we present a new and modular synthetic concept to access novel diazadiborabenzo[b]triphenylenes 7 a–h using the B−N doped biradical 16 as intermediate. Characterization of the photophysical properties revealed the emission spectra of the diazadibora benzo[b]triphenylenes 7 a–h can conveniently be tuned by small changes of the substitution on the boron‐atom. All of the diazadibora compounds show a short life‐time phosphorescence. Additionally, we were able to rationalize the excited‐state relaxation of the diazadiboraacene 7 a via intersystem crossing by quantum chemical calculations. The new synthetic strategy provides an elegant route to various novel B−N doped acenes with great potential for applications in molecular materials. [ABSTRACT FROM AUTHOR]