Electrically conductive PP/EPDM dynamically crosslinked thermoplastic vulcanizate (TPV)/expanded graphite (EG) has been successfully prepared via melt compounding of maleic anhydride grafted polypropylene (PP-g-MA)/EG masterbatch and a commercially available TPV material. Correlation between graphite microstructure, and electrical conductivity as well as melt rheological behavior has been studied. Natural graphite flake (NGF), graphite intercalated compound (GIC), and exfoliated graphite (EG) have been employed and compared. Scanning electron microscopy (SEM) showed the presence of 100-200 nm nanolayers in the structure of PP-g/EG masterbatches, whereas thinner platelets (1.5-2.5 nm) were revealed by transmission electron microscopy (TEM). Better dispersion of the graphite nanolayers in the microstructure of TPV/PP-g-MA/EG composite was verified, as the 7.3 angstrom spacing between the aggregated graphite nanolayers could not be observed in the XRD pattern of this material. TPV/PP-g/EG nanocomposites exhibited much lower conductivity percolation threshold ((p,) with increased conductivity to 10-5 S/cm at EG wt % of 10. Higher nonlinear and nonterminal melt rheological characteristics of dynamic elastic modulus (G') at low frequency region was presented by the TPV/PP-g/ EG nanocomposites, indicating the formation of nanoscopic conducting multiple networks throughout the continuous TPV matrix. Maleated PP was found to be much more effective in separating EG nanolayers which is attributed to the higher interfacial interaction between PP-g-MAH and EG, synergized with its multiporous structure. (c) 2007 Wiley Periodicals, Inc.