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In the present study, dielectric and thermal properties of poly(aryl ether ketone) (PAEK)-nanocomposites with varying weight percentage of magnesium oxide (MgO) have been reported. The thermal properties of PAEK/MgO nanocomposites were studied using differential scanning calorimetry, thermogravimetric analysis, thermo-mechanical analysis and thermal conductivity. Transmission electron microscopy of the developed nanocomposites shows agglomerate-free dispersion of MgO nanoparticles in PAEK matrix. From the dielectric properties, dielectric constant of 13 was achieved for 10 wt% PAEK/MgO nanocomposite at 230°C. Further, minimum tan δ and maximum volume resistivity were found for 10 wt% PAEK/MgO nanocomposite. Data from thermal studies indicate that the incorporation of MgO into PAEK significantly enhanced the glass transition temperature and slightly deteriorated the thermal stability, char yield, and flame-retardant properties. Also, highest thermal conductivity and lowest coefficient of thermal expansion were achieved at 10 wt% of the MgO content. An excellent combination of both dielectric and thermal properties of the PAEK/MgO nanocomposites developed in the present study finds its potential application in microelectronics and electrical insulation in power equipments.