This paper describes the first detailed investigation of the dielectric behavior of liquid solutions of large solute molecules possessing small polar groups capable of rotation about a chemical bond. Three hindered hydroxy-compounds are chosen as examples and their dielectric properties in Decalin solution are measured at frequencies up to 2.4×1010 cps which includes the region of maximum absorption. In each case two distinct absorption regions are obtained, in contrast to the results for the rigid molecule o-dichlorobenzene, which gives a Debye curve with a single relaxation time. A comparison of the calculated and observed dipole moments supports the theory that in each case the lower frequency absorption is due to the rotation of the main part of the molecule and the higher frequency absorption is due mainly to the independent orientation of the hydroxyl group by rotation about the C–O bond. The activation energies and frequency factors for the dielectric mechanisms are determined, where possible, from the displacement of the absorption with temperature. The activation energies for complete molecule rotation and for independent hydroxyl orientation are similar. The frequency factor for the hydroxyl mechanism is larger, however, and this accounts for the higher frequency of the absorption due to this mechanism.