Despite the large number of plausible isomers of benzene (C6H6), only four valence isomers [(CH)(6)] have been experimentally detected, all of which are nonionic and possess skeletal frameworks built from localized C-C bonds. Herein, we present the isolation of a diazatetraborabenzene analogue of a hypothetical zwitterionic valence isomer of benzene. Therein, two electrons are delocalized over the four boron atoms in the six-membered B4N2 ring, which is a result of the sigma-bonding interaction between two odd-electron B-B pi-orbitals. Simple treatment with a crown ether leads to the formation of a paramagnetic potassium-doped radical ion pair that exhibits a thermally populated triplet character.