The salt CF3C(OH)NH2+AsF6- reacts with XeF2 in BrF5 solvent by means of an HF elimination reaction to give the novel xenon-oxygen-bonded CF3C(OXeF)NH2+ cation. Both CF3C(OH)NH2+ and CF3C(OXeF)NH2+ have been characterized in BrF5 solvent using Xe-129, F-19, C-13, and H-1 NMR spectroscopy. Hindered rotation about the C-N bonds in both cations results in chemical inequivalence of the amido protons in the H-1 NMR spectra. Assignment of the amido proton resonances was made using the two-dimensional heteronuclear (H-1-F-19) NOESY technique. The CF3C(OXeF)NH2+ cation is not observed in anhydrous HF solution, but complete removal of the HF solvent in vacuo results in the isolation of CF3C(OXeF)NH2+AsF6- as a white powder which has been characterized by Raman spectroscopy. The Xe-O bond of the CF3C(OXeF)NH2+ cation is interpreted as having substantial covalent character on the basis of trends among Xe-129 and F-19 NMR chemical shifts, (1)J(F-19-Xe-129), and Xe-F stretching frequencies for related xenon(II) species. The substantial covalent character of the Xe-O bond is attributed, in great measure, to pi-bonding between carbon and nitrogen. An intermediate HF solvate, CF3C(OH)NH2+AsF6-.XeF2.xHF, has also been isolated from anhydrous HF at low temperature. Raman spectroscopy indicates that the XeF2 molecule is weakly coordinated to the CF3C(OH)NH2+ cation, possibly through hydrogen-bonding interactions with the protonated carbonyl and/or amino groups. This solvate represents the first example of an isolated intermediate in an HF elimination reaction involving XeF2.