The reaction of atomic boron with benzene in solid neon has been investigated by matrix isolation infrared spectroscopy with isotopic substitutions as well as quantum chemical calculations. The reaction is initiated by boron atom addition to benzene in forming an eta(2)-(1, 4) pi adduct (A). A borepinyl radical (B) formed by C-C bond insertion is also observed on annealing. The eta(2)-(1, 4) pi adduct photoisomerizes to an unprecedented borole substituted vinyl radical intermediate (C) via ring-opening and rearrangement reactions involving an antiaromatic borole subunit. A previously unconsidered 1-ethynyl-2-dihydro-1H-borole radical (D) is generated as the final product under UV light irradiation. The results presented herein give new insight into the benzene carbon-carbon bond cleavage and rearrangement reactions mediated by a nonmetal and provide a possible route for the construction of heterocyclic borepinyl and borole species via benzene ring opening and rearrangement reactions.