The structural characterization and dynamic properties. of solid-state inclusion complexes (ICs) formed-between beta-cyclodextrin (beta-CD; host) and perfluorooctanoic acid (PFOA; guest) were investigated using C-13 NMR spectroscopy. The 1:1 and 2:1 host/guest solid-state complexes were prepared using a modified dissolution method to obtain complexes with high phase purity. These complexes were further characterized using differential scanning calorimetry (DSC), FT-IR spectroscopy, powder X-ray diffraction (PXRD), F-19 direct polarization (DP), and C-13 cross-polarization (CP) with magic-angle spinning (MAS) NMR spectroscopy. The F-19 -> C-13 CP results provided unequivocal support for the formation of well-defined inclusion compounds. The phase purity of the complexes formed between beta-CD and PFOA were assessed using the F DP :NMR,technique at Variable temperature (VT) and MAS at 20 kHz. The complexes were found to be of high phase purity when prepared in accordance with the modified dissolution method. The motional dynamics of the guest in the solid complexes were assessed using T-1/T-2/T-1 rho relaxation NAIR methods at ambient and VT conditions. The relaxation data revealed reliable and variable guest dynamics for the 1:1 versus 2:1 complexes at, the VTs investigated. The motional dynamics of the guest molecules involve an ensemble of axial motions of the whole chain and 120 degrees rotational jumps of the methyl (CF3) group at the termini of the perfluorocarbon chain. The axial and rotational dynamics. of the guest in the 1:1 and 2:1 complexes differ in distribution and magnitude in accordance with the binding geometry of the guest within the lost.