The effect of the polarity of modifier and polymer matrixes on the morphology and interfacial action of nanocomposites was studied by molecular dynamics (MD) and inverse gas chromatography (IGC) based on ethylene-vinyl acetate (EVA)/organic montmorillonite (OMMT), where vinyl acetate (VA) concentrations are 9.3 and 18 wt %, respectively. It is found that EVA with higher VA concentration displays a higher surface energy than that with lower VA concentration. Modifier with two long alkyl tails will lower the surface energy of montrnorillonite (MMT) more effectively. Combined with transmission electron microscopy (TEM) photography of EVA/OMMT nanocomposites, it is found that the surface energies of organic montrnorillonite and EVAs make great contributions to the dispersion of the OMMT in polymer matrixes. OMMT modified by two long alkyl tails displays weaker acid and base properties which will have a better interaction with EVAs through acid-base interaction. Molecular simulation (MD) proved that nonpolar interaction determines the binding between EVAs and organoclays, otherwise electrostatic interaction in polar polymer/organoclay systems. Binding energies were calculated by MD, and the results show stronger interaction between 20A (organoclay made from two long alkyl tails surfactant) and EVA. Interfacial action between filler and polymer matrix should be accountable for the mechanical properties of the nanocomposite.