Inverse gas chromatography (IGC) was applied to characterize the surface of kaolinite. The adsorption thermodynamic parameters (the standard enthalpy (∆H0), entropy (∆S0) and free energy of adsorption (∆G0), the dispersive component of the surface energy (γsd), and the acid/base character of kaolinite surface were estimated by using the retention time of different non-polar and polar probes at infinite dilution region. The specific free energy of adsorption (∆Gsp), the specific enthalpy of adsorption (∆Hsp), and the specific entropy of adsorption (∆Ssp) of polar probes on kaolinite were determined. (∆Gsp) values were correlated with the donor and modified acceptor numbers of the probes to quantify the acidic (KA) and the basic (KD) parameters of the kaolinite surface. The values obtained for the parameters KA and KD indicated a basic character for kaolinite surface.