Positive temperature coefficient to resistivity (PTCR) characteristics of polystyrene (PS)/Ni‐powder (40 wt%) composites in the presence of multiwall carbon nanotubes (MWCNTs) has been investigated with reference to PS/carbon black (CB) composites. The PS/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈110°C, above the glass transition temperature (Tg) of PS (Tg ≈95°C). Interestingly, the PTC trip temperature of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites appeared at ≈90°C (below Tg of PS), indicating better dimensional stability of the composites at PTC trip temperature. The PTC trip temperature of the composites below the Tg of matrix polymer (PS) has been explained in terms of higher coefficient of thermal expansion (CTE) value of PS than Ni that led to a disruption in continuous network structure of Ni even below the Tg of PS. The dielectric study of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites indicated possible use of the PTC composites as dielectric material. Dynamic mechanical analysis (DMA) and thermogravimetric analysis studies revealed higher storage modulus and improved thermal stability of PS/Ni‐powder (40 wt%)/MWCNT (0.75 phr) composites than the PS/CB (10 wt%) composites. POLYM. COMPOS., 33:1977–1986, 2012. © 2012 Society of Plastics Engineers