Substitution of a C=C bond by an isoelectronic B–N bond is a well-established strategy to alter the electronic structure and stability of acenes. BN-substituted acenes that possess narrow energy gaps have attractive optoelectronic properties. However, they are susceptible to air and/or light. Here we present the design, synthesis and molecular structures of fully π-conjugated cationic BN-doped acenes stabilized by carbodicarbene ligands. They are luminescent in the solution and solid states and show high air and moisture stability. Compared with their neutral BN-substituted counterparts as well as the parent all-carbon acenes, these species display improved quantum yields and small optical gaps. The electronic structures of the azabora-anthracene and azabora-tetracene cations resemble higher-order acenes while possessing high photo-oxidative resistance. Investigations using density functional theory suggest that the stability and photo-physics of these conjugated systems may be ascribed to their cationic nature and the electronic properties of the carbodicarbene.