The generation of 1,2‐azaborine (4), the BN‐analogue of ortho‐benzyne, was recently achieved by elimination of tert‐butyldimethylchlorosilane under the conditions of flash vacuum pyrolysis. The present investigation identifies by computational means pathways for the thermal isomerization and fragmentation of 1,2‐azaborine. The computations were performed using single reference (hybrid/density functional, second order Møller‐Plesset perturbation, and coupled cluster theories) as well as multiconfiguration methods (complete active space SCF based second order perturbation theory, multireference configuration interaction, and multiconfiguration coupled electron pair approximation) with basis sets up to polarized triple‐ζ quality. The 1,2‐azaborine is, despite the distortion of its molecular structure, the most stable C4H4BN isomer investigated. The formation of BN‐endiyne isomers is highly unfavorable as the identified pathways involve barriers close to 80 kcal mol−1. The concerted fragmentation to ethyne and 2‐aza‐3‐bora‐butadiyne even has a barrier close to 120 kcal mol−1. The fragmentation of BN‐enediynes has energetic requirements similar to enediynes. © 2015 Wiley Periodicals, Inc.