Results of the first solid-state Xe-131 NMR study of xenon-containing compounds are presented. The two NMR-active isotopes of xenon, Xe-129 (I = 1/2) and Xe-131 (I = 3/2), are exploited to characterize the xenon magnetic shielding and quadrupolar interactions for two sodium perxenate salts, Na4XeO6 center dot xH(2)O (x = 0, 2), at an applied magnetic field strength of 11.75 T. Solid-state Xe-129/131 NMR line shapes indicate that the local xenon environment in anhydrous Na4XeO6 adopts octahedral symmetry, but upon hydration, the XeO64- anion becomes noticeably distorted from octahedral symmetry. For stationary, anhydrous samples of Na4XeO6, the heteronuclear Xe-129/131-Na-23 dipolar interaction is the principal contributor to the breadth of the Xe-129/131 NMR lines. For stationary and slow magic-angle-spinning samples of Na4XeO6 center dot 2H(2)O, the anisotropic xenon shielding interaction dominates the Xe-129 NMR line shape, whereas the Xe-131 NMR line shape is completely dominated by the nuclear quadrupolar interaction. The xenon shielding tensor is approximately axially symmetric, with a skew of -0.7 +/- 0.3, an isotropic xenon chemical shift of -725.6 +/- 1.0 ppm, and a span of 95 +/- 5 ppm. The Xe-131 quadrupolar coupling constant, 10.8 +/- 0.5 MHz, is large for a nucleus at a site of approximate O-h symmetry, and the quadrupolar asymmetry parameter indicates a lack of axial symmetry. This study demonstrates the extreme sensitivity of the Xe-131 nuclear quadrupolar interaction to changes in the local xenon environment.