EPR spectra of cyclodextrins labelled with TEMPO derivatives (SL-CDs) are sensitive to complexation with large guest molecules. We used SL-CDs to explore the behaviour of concentrated PEG/PPG solutions. The relationship between rotational correlation times and solvent viscosity showed significant deviations from the Debye-Stokes-Einstein equation, probably due to self-aggregation of alkylene glycols in concentrated solutions. The data fit the fractional Debye-Stokes-Einstein equation well. We have also studied complexation of SL-CDs with adamantane-functionalised DAB dendrimers. The strength of binding increases with dendrimer generation; formation of supramolecular aggregates at high concentrations was observed with the generation 3 dendrimer.