This paper presents the speed of sound in selected glymes (monoglyme, diglyme, triglyme and tetraglyme) in N,N-dimethylformamide + water mixed solvent at four temperatures: 293.15 K, 298.15 K, 303.15 K and 308.15 K. The data obtained were used to calculate the values of isentropic compressibility (κS) of glymes solutions and apparent molar isentropic compression (KS,Φ,m), as well as the limiting partial molar isentropic compression (KS,m0) of glymes in the mixed solvent (DMF + W). Changes in the obtained values of the physicochemical parameters, as functions of temperature or mole fraction of water in the mixed solvent, were analyzed in terms of the molecular interactions and structural differentiation of the investigated systems. The hydrophobic hydration process of the studied glymes is visible in the high water content area of the mixed solvent. The hydration number of glymes in water at four temperatures was calculated and analyzed.