The use of SF6 as a spy molecule in solution-state NMR is investigated as an alternative to Xe-129 NMR. F-19 chemical shift, longitudinal relaxation time, and integral measurements, as well as intermolecular nuclear Overhauser effects, are reported for SF6 dissolved in simple deuterated solvents and/or in various solutions among which are aqueous Solutions of cucurbit[6]uril (CB) and alpha-cyclodextrin (alpha CD). Both CB and alpha CD form a 1:1 inclusion complex with SF6. In a 0.2 M D2SO4-D2O solution, the affinity of CB for SF6 is 2.9 x 10(5) L mol(-1) at 298 K; it is the largest value ever found for the inclusion of a neutral guest into the CB cavity. It is one order of magnitude larger than in a 0.2 M Na2SO4-D2O solution, and the role of the cation is evidenced. In D2O, the affinity of alpha CD for SF6 is about 25 L mol(-1). With CB, the kinetics is slow on both the H-1 and F-19 chemical shift time scales, while with alpha CD fast exchange is observed. The F-19 chemical shift of SF6 is much less sensitive to medium effects than the chemical shift of Xe-129. This might be a limitation if minute structural changes are to be investigated but, in the present study, turned out to be an advantage for determining the affinity of alpha CD for SF6. With CB, the F-19 chemical shift of included SF6 is found to be sensitive to the nature of the cation bound at the portals. The F-19 relaxation time of SF6 dissolved in deuterated solvents is dominated by the spin-rotation mechanism and is orders-of magnitude shorter that the Xe-129 relaxation time. It is found to be rather sensitive to the environment and was used to determine the affinity of alpha CD for SF6. The detection limit of SF6, by F-19 NMR is lower than the NMR detection limit of thermally polarized Xe-129 by more than three orders of magnitude. It lies in the micromolar range, and SF6 concentrations of the order of 10 mu M were determined by F-19 NMR signal integral measurements and used to quantify the affinity of CB for SF6. Integrals, which are usually not reliable for quantitative measurements in Xe-129 NMR, were proven to be highly valuable for determining the affinity of alpha CD for SF6 as well. Most interestingly, heteronuclear Overhauser effect measurements allow to selectively highlight the H-1 of a SF6 binding site according to the F-19-H-1 proximity and were used to characterize the inclusion complex formed with alpha CD.