The synthesis of a new family of iodonium zwitterions, in which the formal anion is a trifluoroborate moiety, is reported. These reagents present very good stability and have high resistance toward benzyne formation. Their structures were confirmed by X-ray crystallographic analysis and were further investigated using DFT calculations. QTAIM analysis supports an ionic, noncovalent, I+···BF3- interaction, in accordance with a true zwitterionic nature. Preliminary results of synthetic applications, the arylation of phenolates and trifluoroborate group functionalization, are reported.