Two novel boron heterocyclic radicals, an addition bicyclo[4.2.1]octa-1,3,5-trien-1-yl-borane radical (A) and an insertion 7-1H-borolo[1,2-a]borinine radical (B), were synthesized, and characterized in the reaction of atomic boron with benzocyclobutene. Species B involving a fused boron heterocyclic was spectroscopically characterized for the first time. This work is a new approach for boron-mediated molecular editing and the synthesis of fused boron heterocyclic compounds.