The effect of Lucentite (TM) STN nanoclay on the relaxation behavior of poly(vinylidene fluoride) (PVDF) nanocomposites was investigated using dielectric relaxation spectroscopy (DRS), and wide- and small-angle X-ray scattering. Lucentite (TM) STN is a synthetic nanoclay based on hectorite structure containing an organic modifier between the hectorite layers. The addition of this nanoclay to PVDF results in preferential formation of the beta-crystallographic phase. When the STN content increased to 5% and 10%, only the beta-phase was observed Bragg long period and lamellar thickness both decrease with STN addition The relaxation rates for processes termed alpha(a) (glass transition, related to polymer chain motions in the amorphous regions) and alpha(c) (related to polymer chain motions in the crystalline regions and fold surfaces) can be described either with the Vogel-Fulcher-Tamman equation or with Arrhenius behavior, respectively. DRS shows that the alpha(a) relaxation rate increases with the concentration of STN because of the reduction of intermolecular correlations between the polymer chains, caused by the presence of layered silicate nanoclay particles, which serve to segregate polymer chains in the amorphous regions. Comparing samples with beta-crystal phase dominant, the relaxation rate for the alpha(c) relaxation also increases with concentration of STN in all nanocomposite samples. Dielectric properties at low frequencies are dominated by the dc conductivity, and as more STN is added, the conductivity increases rapidly The addition of 10% STN makes the dc conductivity increase by almost four decades when compared with neat PVDF. (C) 2009 Wiley Periodicals, Inc J Polym Sci Part B Polym Phys 47 2520-25327 2009