This report presents the preparation and characterization of a xenon-containing cationic radical species, XeOO+. The XeOO+ cation was produced either by co-deposition of the reactive species generated by laser ablation of different transition metals with dioxygen and xenon mixtures in excess argon or by condensation of high-frequency discharged O2/Xe/Ar mixtures at 12 K and is identified by infrared absorptions. High-level quantum chemical calculations indicate that XeOO+ has a bent structure with direct xenon-oxygen dative bonding, and the doublet ground state is much more stable than the Xe + O2+ reactants.