Electrolytic conductivities of potassium halides, KX (X = Cl−, Br−, I−) have been investigated in 10, 20, and 30 mass% glycerol + H2O mixtures at 298.0, 308.0, and 318.0 K. The conductance data have been analyzed by the Fuoss-conductance–concentration equation in terms of the limiting molar conductance (Λ0), the association constant (K A ), and the distance of closest approach of ion (R). The association constant (K A ) tends to increase in the order: 10 mass% < 20 mass% < 30 mass% glycerol + water mixtures, while it decreases with temperature. Thermodynamic parameters ΔH 0, ΔG 0, and ΔS 0 are obtained and discussed. Also, Walden products (Λ0η) are reported. The results have been interpreted in terms of ion–solvent interactions and structural changes in the mixed solvents.