One- and two-dimensional xenon-129 nuclear magnetic resonance (Xe-129 NMR) experiments were performed on a series of poly(2,6-dimethyl-1,4-phenylene oxide) (PXE) samples to characterize the sorption environments and the relative mobility of xenon in the samples. Samples of PXE in sealed NMR tubes pressurized with xenon were studied as a function of temperature, pressure, and processing. In a dense cast film of PXE, the shift relative to the free gas resonance is smaller than that observed for typical glassy polymers, indicating a higher free volume environment. Solubility rises rapidly as temperature decreases. The lower shift and rapid increase in solubility with decreasing temperature are consistent with a relatively high free volume environment for gas sorption. If PXE is antiplasticized, the shift is slightly larger, the increase in signal intensity with decreasing temperature is smaller, and the line widths are greater. This sample is a better packed glass with less free volume and slower diffusion. Samples of PXE produced by rapid precipitation have broad lines and even lower shifts corresponding to a wide distribution of higher free volume environments. The appearance of two lines at low temperatures is consistent with the presence of a bimodal distribution of environments similar to what has been observed with positron annihilation lifetime spectroscopy. The resonance closest to the free gas resonance is associated with very large free volume elements relative to those of traditional glassy polymers. In two-dimensional experiments, there is a rapid exchange of xenon by diffusion between the two environments, indicating the close spatial proximity of the environments. Two-dimensional experiments and one-dimensional progressive saturation experiments reflect a rapid exchange of xenon between the sorbed state and the free gas resonance for the precipitated samples. At low temperatures, the high field peak exchanges more rapidly with the free gas.