AbstractWe report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser‐polarized xenon gas. Both areas utilize the pulsed gradient spin‐echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self‐diffusion coefficients—a brief overview of this area is provided in the Introduction. The heterogeneous or multiple‐length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time‐dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long‐time asymptote, with the aim of understanding the long‐length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long‐time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono‐sized glass beads. The Padé approximation is used to interpolate D(t) data between the short‐ and long‐time limits. Initial studies of continuous flow laser‐polarized xenon gas demonstrate velocity‐sensitive imaging of much higher flows than can generally be obtained with liquids (20–200 mm s−1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s−1 owing to the high diffusivity of gases compared with liquids. We also present the first gas‐phase NMR scattering, or diffusive‐diffraction, data, namely flow‐enhanced structural features in the echo attenuation data from laser‐polarized xenon flowing through a 2 mm glass bead pack. Copyright © 2002 John Wiley & Sons, Ltd.