Advancing the practical applications of surface-modified nanoparticles requires that their dispersion in solvents can be controlled. The degree of dispersion depends on the affinity between surface-modified nanoparticles and solvents, which can be quantified using the work of adhesion at the interface. Herein, the affinity between a surface-modified inorganic solid and an organic solvent was evaluated by calculating the work of adhesion at the interface. The phantom-wall method, which is a thermodynamic route for evaluating the work of adhesion at an interface using molecular dynamics simulations, was applied to the decanoic acid-modified Al2O3/hexane interface. Molecular dynamics simulations were performed for flat interface systems to focus on the interactions between substances that affect the affinity on the surface. As a result, the surface coverage of decanoic acid was found to affect the work of adhesion, with a maximum value of 45.66 ± 0.75 mJ/m2 at a surface coverage of 75%. An analysis of the mass density profiles of Al2O3, decanoic acid, and hexane in the vicinity of the interface showed that the increase in the work of adhesion with the surface coverage was due to the penetration of hexane molecules into the decanoic acid layer on the Al2O3 surface. At a surface coverage of 75%, some hexane molecules were trapped in the layer of oriented decanoic acid molecules. These results suggested that the interfacial affinity can be enhanced by controlling the surface modification so that the solvent can penetrate the layer of the modifier.