The introduction of the concept of surface properties can help us to better analyze the basic physicochemical property changes of metal-organic framework (MOF) materials before and after fluorine functional group treatment. In this study, several polar and nonpolar probes were selected to determine the surface properties, including surface-dispersive free energy, Lewis acid-base constants of Ni-MOF-74, and perfluoro carboxylic acid-modified Ni-MOF-74-Fn (n = 3, 5, and 7) in the range of 343.15-383.15 K by inverse gas chromatography (IGC). It was observed that the surface energy of the treated Ni-MOF-74-Fn showed a substantial decrease with the growth of the perfluorocarbon alkyl chains and the increase in surface roughness. In addition, Lewis acidic sites exposed by the Ni-MOF-74 material after adopting modification with fluorine functional groups increased with the increase of perfluorinated carboxylic acid chains, and their surface properties changed from amphiphilic acidic to strongly acidic. These results not only enrich the basic physical property data of Ni-MOF-74 but also provide more theoretical basis for the fluorinated functionalized custom-designed MOFs and enrich their applications in the fields of multiphase catalysis, gas adsorption, and chromatographic separation.