Borylated triazenes were synthesized by the dehydrocoupling of triazenes with 9-borabicyclo(3.3.1)nonane, by the condensation of triazenes with BEt3, or by the reaction of sodium triazenides with dialkyl- or diarylboron halides. The structures of the products were found to depend on the size of the substituents. Sterically demanding mesityl groups at boron or nitrogen gave rise to open-chain structures, whereas smaller substituents led to the formation of novel BN3 heterocycles.