In order to explain the behavior of solutes in water + ethanol mixtures, the thermodynamic and NMR spectroscopic properties of the ternary solutions containing urea, sucrose and 1-phenyl-2-thiourea solutes in water + ethanol mixtures were investigated. The density, enthalpy of solution Delta(sol)H and H-1-NMR spectral measurements were carried out at 298.15 K, and the partial molar volumes of the solutes V-3(infinity) and chemical shift delta were estimated. The V-3(infinity) values for sucrose and 1-phenyl-2-thiourea are almost independent of the mole fraction of water in the water + ethanol mixture x(1), although that for urea shows a complicated concentration dependence at higher x(1) values. The Delta(sol)H values were endothermic for all systems. The absolute values of Delta(sol)H for sucrose and 1-phenyl-2-thiourea increased rapidly on increasing the concentration of poor pure solvent, but that for urea showed a maximum at x(1) = 0.9. The delta values for water and ethanol were not affected by adding a small amount of solute. The delta values for the solute depend on x(1) in the same manner as that of the -CH2-proton of ethanol. These results suggest that sucrose and 1-phenyl-2-thiourea are distributed selectively in water or ethanol aggregates in the water + ethanol mixture, respectively, and, however, that urea is distributed in the mixed solvent with a fluctuated structure.