Stable hypervalent bromine(III) compounds were synthesized via aryl bromine oxidation with sp-hybridized nitrogen cations generated by oxime N-O bond cleavage in trifluoroacetic acid. The resulting intramolecular N-Br hypervalent bond is effectively stabilized by the planar xanthone structure. The structures and physicochemical properties of these λ3-bromanes were characterized by X-ray crystallography, cyclic voltammetry, UV-vis spectroscopy, and computational analysis.