Dielectric studies of poly(vinyl pyrrolidone)/ethyl alcohol (PVP-E) binary mixtures with concentration variations were carried out in the frequency range of 10 MHz to 10 GHz by time domain reflectometry at 15, 25, 35, and 45 degrees C. One relaxation process, corresponding to ethyl alcohol molecules in the poly(vinyl pyrrolidone) (PVP) matrix, was observed in this frequency range for all the mixtures. The static dielectric constant of the PVP-E mixtures decreased linearly with an increase in the weight fraction of PVP. The observed anomalous increase in the value of the relaxation time (7) of these mixtures was interpreted by the consideration of the variation in the local structure of self-associated ethyl alcohol molecules and also the PVP behavior as a geometric constraint for the rotational motion of ethyl alcohol molecules. Furthermore, the tau values of these mixtures were independent of the viscosity. The energy parameters for the dielectric relaxation process (the free energy, enthalpy, and entropy of activation for the dipolar orientation) were determined to confirm the transient behavior of the heterogeneous species due to the breaking and re-forming of hydrogen bonds with the internal rotation of -OH groups in the ordered structure of the PVP-E mixtures. On the basis of the evaluated dielectric parameters, the formation of supermolecular structure in the PVP-E mixtures in dynamic equilibrium was sketched and examined by the consideration of the hydrogen bonding between the terminal hydroxyl groups of self-associated ethyl alcohol flexible chains and the carbonyl groups of monomer units of PVP coiled chains. (c) 2005 Wiley Periodicals, Inc.