The structure of ZnMgAl hydrotalcite-like compounds (ZnMgAl-HTLC) prepared by hydrothermal synthesis was studied by X-ray diffraction (XRD). With a series of polar and nonpolar molecules as probes, inverse gas chromatography (IGC) was used to measure the surface properties of ZnMgAl-HTLC. It was found that the XRD pattern of ZnMgAl-HTLC was narrow, sharp and high. The results showed that ZnMgAl-HTLC with a higher purity was obtained by hydrothermal synthesis. The surface adsorption free energy was less than zero. The surface dispersive free energy was 6.02 mJ/m2. The acid-base interaction free energy was 5.33 kJ/mol. The adsorption enthalpy was 43.6 kJ/mol, and the adsorption entropy was 0.15 kJ/mol. The IGC method is significant in the study of the surface properties of ZnMgAl-HTLC.