The complexation of sulfur hexafluoride (SF6), a highly potent greenhouse gas, by cucurbit[6]uril (CB) was studied at various temperatures in Na2SO4 aqueous solutions by F-19 and H-1 NMR. CB shows a remarkable affinity for SF6, suggesting that it is a suitable molecular container for the design of materials tailored for SF6 trapping. At 298 K, the equilibrium constant characterizing the inclusion of SF6 by CB is 3.1 x 10(4) M-1 and the residence time of SF6 within the CB cavity is estimated to be of the order of a few seconds. The enthalpic and entropic contributions to the free energy of encapsulation were determined and are discussed. This work also reports on the interest of SF6 in the framework of the spin-spy methodology. The advantages and drawbacks of solution-state F-19 NMR of SF6 with respect to Xe-129 NMR are discussed. SF6 comes forward as a versatile and informative spin-spy molecule for probing systems in solution because its detection limit by F-19 NMR reaches the micromolar range with standard equipment and because quantitative integral measurements, relaxation time measurements, and demanding experiments, such as translational diffusion coefficient measurements, are easily carried out in addition to chemical shift measurements. Solution-state F-19 NMR of SF6 emerges as a promising alternative to Xe-129 NMR for probing cavities and for other applications relying on the encapsulation of an NMR active gaseous probe.