The effect of excess excitation energy on the rotational dynamics of rhodamine 6G in the ground and the first singlet excited state has been investigated in series of n-alcohols and alkanenitriles using the picosecond polarization grating technique. In nitriles, the reorientation times are the same for excitation at the S1 ← S0 and S2 ← S0 transitions, and no state dependence could be detected. In alcohols, the rotational dynamics of rhodamine 6G in the excited state is about 25% faster when formed with 1.15 eV excess excitation energy. This effect is ascribed to a decrease of the hydrodynamic volume due to dissociation of solute/solvent hydrogen bond following intramolecular vibrational redistribution. An accompanying perturbation of the solvent shell structure caused by the fast local temperature jump is not excluded.