A series of diphosphine Pt(II) aryl iodo complexes were reacted with XeF2 to cleanly produce the corresponding Pt(II) difluoro complexes and free iodoarenes. However, when aryl ligands bearing fluoro substituents in the ortho positions were used, the formation of the corresponding Pt(II) aryl fluoro complexes was observed in the reaction with XeF2. In the case of the Pt-C6F5 complex, the products of the fluoride-for-iodide exchange were the only products observed by means of P-31 and F-19 NMR spectroscopy. The experimental and theoretical studies suggest that the formation of iodine-fluorine bond may accompany this transformation. The plausible "I-F" species could be trapped by electron-richer organoplatinum complexes to give a Pt(IV) transient which subsequently eliminates the corresponding aryl iodide. Hence, in some cases a pathway involving an attack of XeF2 at the iodo ligand of Pt(II) aryl iodo complexes to generate I-F species can be operative in addition to or instead of the XeF2 attack at the metal center. Our DFT studies demonstrate that the electrophilic attacks of XeF2 at both sites, platinum and iodide, can be competitive.