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Inverse gas chromatography was applied to evaluate the surface thermodynamic properties of biodegradable poly (caprolactone) diol (PCLD) in the temperature range 313.15–333.15 K with steps of 5 K. The net retention volumes, VN, were determined for the n-alkanes and polar solute probes. Dispersive surface free energy,, was calculated using the Schultz and Dorris-Gray methods, and at T= 313.15 K the values were found to be 19.87 and 21.61 mJm− 2 respectively. The dispersive free energy decreased with increase in temperature. Surface Lewis acid parameter, K a, and Lewis base parameter, K b, were calculated following Gutmann’s approach. The K a and K b values were found to be 0.212 and 0.593 respectively, which revealed the basic nature of PCLD. The three components of the Hansen solubility parameters were determined using for the PCLD surface, and their variation with temperature was studied.