TEMPO-based spin probes and β-cyclodextrin form 1 ∶ 2 guest–host complexes in viscous aqueous glycerol solutions at low temperatures. The spin probe mobility in these complexes is much higher than in the bulk glassy solution. The similar tumbling rates of the spin probe in viscous host–guest complexes and in solvent-free complexes suggest that the complexation effectively shields the nitroxide unit from the solvent molecules. This is consistent with the low activation barrier for molecular tumbling of immobilised label.