The present study investigates the effect of the carboxylated multi-walled carbon nanotube (0~3 wt %) content on the electrical and thermal properties of high density polyethylene/carbon black/carboxylated multi-walled carbon nanotube (HDPE/CB/c-MWNT) hybrid nanocomposites. The room temperature electrical resistivity and positive temperature coefficient (PTC) intensity of the nanocomposites significantly improved with the addition of c-MWNT. However, the heat of fusion decreases as the amount of c-MWNT increases. Further, the microstructural parameters such as the fractional free volume (Fv) and free volume hole size (Vf) of the nanocomposites shows appreciable changes around the percolation threshold. Secondly, the PALS results seem to correlate well with the electrical and thermal properties of the composites.