This study investigates the dielectric properties of multiwalled carbon nanotube (MWCNT)/polystyrene (PS) composites over the broadband frequency range, i.e., 10−1 to 106 Hz. The results showed that the real permittivity and imaginary permittivity increased remarkably with increased MWCNT concentration. For instance, at 100 Hz, the real permittivity and imaginary permittivity of the pristine PS was 2.71 and 0.01, respectively, which increased to 5.22 × 104 and 3.28 × 107 at 3.50 wt%, respectively. The increase in the real permittivity was related to the formation of a large number of nanocapacitor structures, i.e., MWCNTs as nanoelectrodes and polymer matrix as dielectric material, i.e., interfacial polarization. The increase in the imaginary permittivity with MWCNT loading was attributed greater number of dissipating charges, enhanced conductive network formation, and boosted polarization loss arising from interfacial polarization. It was also observed that the real and imaginary permittivities were frequency independent in the insulative region, whereas they decreased drastically with frequency in the conductive region. The descending trend of real permittivity with frequency in the conductive region was related to charge polarization relaxation, whereas the reduction in imaginary permittivity with frequency was attributed to lower Ohmic loss and polarization loss. POLYM. ENG. SCI., 55:173–179, 2015. © 2014 Society of Plastics Engineers