Nanocomposites made of linear low density polyethylene (LLDPE) and organo-modified montmorillonite (O-MMT) were processed by melt compounding from a commercially available premixed LLDPE/nanoclay masterbatch, at different nanoclay loadings, by co-rotating twin-screw extruder. The morphological and dielectric properties of LLDPE/O-MMT nanocomposites were investigated to understand the structure-dielectric properties relationship in the nanocomposites. The microstructures of the materials were characterized by wide angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Initial findings by FTIR spectroscopy characterization indicated the absence of any chemical interaction between LLDPE and nanoclay during the extrusion process, while DSC showed that a 1% wt loading of nanoclay particles increased the degree of crystallinity of the nanocomposites samples. On the other hand, XRD, SEM, TEM and AFM indicated that nanoclay layers were intercalated or exfoliated in the LLDPE matrix. A correlation between the structure and dielectric properties of LLDPE/O-MMT nanocomposites was found and discussed.