Composites with nickel particles coated multiwalled carbon nanotubes (Ni-MWNTs) embedded into polyvinylidene fluoride (PVDF) were prepared by solution blending and hot-press processing. The morphology, structure, crystallization behavior, and dielectric properties of composites were studied. The results showed that the crystallization of PVDF was affected by Ni-MWNTs. With the increment of Ni-MWNTs, the content of -phase in PVDF increased. The dielectric permittivity was as high as 290 at 10(3) Hz when the weight fraction of Ni-MWNTs was 10%. The results can be explained by the space charge polarization at the interfaces between the insulator and the conductor, and the formation of microcapacitance structure. (c) 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3746-3752, 2013