A recent report claims to have prepared [F-18]XeF2 by exchange between a large stoichiometric excess of XeF2 and no-carrier-added F-18(-), as salts of the [2,2,2-crypt-M+] (M = K or Cs) cations, in CH2Cl2 or CHCl3 solvents at room temperature. Attempts to repeat this work have proven unsuccessful and have led to a critical reinvestigation of chemical exchange between fluoride ion, in the form of anhydrous [N(CH3)(4)]-[F] and [2,2,2-crypt-K][F], and XeF2 in dry CH2Cl2 and CH3CN solvents. It was shown, by use of F-19 and H-1 NMR spectroscopies, that [2,2,2-crypt-K][F] rapidly reacts with CH3CN solvent to form HF2-, and with CH2Cl2 solvent to form HF2-, CH2CIF, and CH2F2 at room temperature. Moreover, XeF2 rapidly oxidizes 2,2,2-crypt in CH2Cl2 solvent at room temperature to form HF and HF2-. Thus, the exchange between XeF2 and no-carrier-added F-18(-) reported in the prior work arises from exchange between XeF2 and HF/HF2-, and does not involve fluoride ion. However, naked fluoride ion has been shown to undergo exchange with XeF2 under rigorously anhydrous and HF-free conditions. A two-dimensional F-19-F-19 EXSY NMR study demonstrated that [N(CH3)(4)][F] exchanges with XeF2 in CH3CN solvent, but exchange of HF2- with either XeF2 or F- is not detectable under these conditions. The exchange between XeF2 and F- is postulated to proceed by the formation of XeF3- as the exchange intermediate.