Poly(arylene ether nitriles) (PEN) containing various contents of graphene nanosheets (GNs) was prepared via solution-casting method and investigated for their dielectric, mechanical, thermal, and rheological properties. For PEN/GNs nanocomposite with 5 wt % GNs, the dielectric constant was increased to 9.0 compared with that of neat PEN (3.1) and dielectric losses of all nanocomposites were in the range of 0.019–0.023 at 1 kHz. The tensile modulus and strength were increased about 6 and 14% with 0.5% GNs, respectively. The fracture surfaces of the all PEN/GNs nanocomposites revealed that GNs had good adhesion to PEN matrix. The thermal properties of the nanocomposites showed significant increase with increasing GN loading. For 5 wt % GNs-reinforced PEN nanocomposite, the temperatures corresponding to a weight loss of 5 wt % (Td5%) and 30 wt % (Td30%) increased by about 20 and 13°C, respectively. Rheological properties of the PEN nanocomposites showed a sudden change with the GN fraction and the percolation threshold was about 1 wt % of GNs. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012