Four kinds of nylon 6/POSS nancomposites films were synthesized by the phase inversion process. X-ray diffraction (XRD), differential scanning calorimetry (DSC) and water contact angle (CA) measurements were used to characterize the interactions between POSS and PA6 chains. It was demonstrated that the interactions between octaammonium POSS (OA-POSS) and PA6 chains was the greatest compared with aminopropylisobutyl POSS (AB-POSS), aminopropylphenyl POSS (AP-POSS), and Octamethyl POSS (OM-POSS). OA-POSS could achieve the uniformed dispersion state in PA6 matrix. Scanning electron microscopy (SEM), energy dispersive X-ray (EDX) and polarized optical microscopy (POM) were used to investigate the migration behaviors of POSS. X-ray photoelectron spectroscopy (XPS) was qualitatively used to study the migration behaviors as well. It was found that OA-POSS has the greatest migration behaviors compared with other POSS. Finally, proposed migration mechanism was discussed. Crown Copyright (C) 2013 Published by Elsevier B.V. All rights reserved.