A new and generally applicable approach for the gas-phase synthesis of charged phenyl radicals is described. Reaction of nucleophiles with the radical cations of dihalobenzenes in a Fourier transform ion cyclotron resonance mass spectrometer leads to ipso-substitution of a halogen atom. Collisional activation df the resulting ion induces loss of the remaining halogen atom to yield a phenyl radical with a charged substituent. This method was used to generate a series of novel charged phenyl radicals that were purified by ejecting unwanted ions from the cell, and verified to be stable and to have spatially separated charge and radical sites. The reactivity of these charged radicals closely resembles that of the neutral phenyl radical; For example, the radicals abstract an iodine atom from allyl iodide and a thiomethyl radical from dimethyl disulfide, and the rates of these reactions are enhanced by additional electron-withdrawing substituents.