A microemulsion polymerization method was used to achieve better compatibility between polystyrene (PS)/multiwalled carbon nanotubes (MWCNTs) nanocomposites and the host PS matrix to form films with excellent electrical and thermal properties. The films were prepared by embedding the PS/MWCNTs nanocomposite into the PS matrix. The MWCNTs were functionalized with PS nanoparticles to avoid the phase separation problem between the filler and host matrix and to enhance the good dispersibility of MWCNTs in the PS host matrix. The confirmation of the synthesis was analyzed by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and Raman spectroscopy. The variation effect of the PS-linking density on the MWCNT was revealed by scanning electron microscopy and transmission electron microscopy. An enhancement of the thermal and mechanical properties was revealed by thermal gravimetric analysis, differential scanning colorimetric analysis, and dynamic mechanical analysis. POLYM. ENG. SCI., 2013. (c) 2012 Society of Plastics Engineers