Many efforts have been performed on the poly(vinylidene fluoride), PVDF, due to its piezoelectric, pyroelectric and ferroelectric potentials. In this regard, how to fabricate the PVDF with high content of beta-phase, which is also the direct contribution to PVDFs prominent property, becomes a critical issue. In this study, starting with the alpha-phase dominated sample, the PVDF with extremely high content of beta-crystalline phase was obtained by the incorporation of multiwalled carbon nanotubes (MWCNTs) modified by hyperbranched copolymers (HBCs). We proved that, via XRD. DSC as well as the structural characterizations from the polarized optical microscopy and transmission electron microscopy (TEM), the success of this strategy was ascribed to the enhanced dispersibility and stability of MWCNTs endowed by the HBCs, which significantly favors the formation of the beta-crystalline phase of PVDF. (C) 2011 Elsevier Inc. All rights reserved.