Xenon hexafluoride can be prepared by heating of XeF2 at about 300 °C under 6 MPa (60 atmospheres) of fluorine.

VSEPR theory predicts that due to the presence of six fluoride ligands and one lone pair of electrons the structure lacks perfect octahedral symmetry, and indeed electron diffraction combined with high-level calculations indicate that the compound's point group is C3v.

[4] 129Xe and 19F NMR spectroscopy indicates that in solution the compound assumes a tetrameric structure: four equivalent xenon atoms are arranged in a tetrahedron surrounded by a fluctuating array of 24 fluorine atoms that interchange positions in a "cogwheel mechanism".

[6] Xenon hexafluoride hydrolyzes, ultimately affording xenon trioxide:[7] XeF6 is a Lewis acid, binding one and two fluoride anions: Salts of the octafluoroxenate(VI) anion (XeF2−8) are very stable, decomposing only above 400 °C.

[8][9][10] This anion has been shown to have square antiprismatic geometry, based on single-crystal X-ray counter analysis of its nitrosonium salt, (NO)2XeF8.