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Net retention volumes, V_N, of n-alkanes and five polar solute probes on cellulose acetate butyrate – Polycaprolactonediol have been determined by inverse gas chromatography technique in the temperature range 323.15–393.15 K. The V_N values of n-alkanes are used to calculate the dispersive component of surface energy of the blend. The values are decreasing nonlinearly with increase of temperature. The V_N values of the five polar solutes are used to calculate the specific components of the enthalpy of adsorption and entropy of adsorption . The values are used to calculate Lewis acidity constant and basicity constant, which are 0.143 and 0.744, respectively.