The effect of the work of adhesion between carbon blacks and different thermoplastic polymers on the positive temperature coefficient (PTC) of composites was investigated. Thermoplastic polymers, such as EVA, LDPE, LLDPE, HDPE, and PP, were used with the addition of 30 wt% of carbon blacks. The work of adhesion based on the surface free energy of a composite was studied in the context of two-liquid contact angle measurements using deionized water and diiodomethane. It was observed that the resistivity on PTC behavior was greatly increased near the crystalline melting temperature, due to the thermal expansion of polymeric matrix. It was shown that the PTC intensity defined as the ratio of the maximum resistivity (rho(max)) to the resistivity at room temperature (rho(RT)) had the largest value on CB/HDPE composites. From the experimental results, the decrease in the work of adhesion induced by interactions between carbon black surfaces and polymer chains is an important factor in the fabrication of a PTC composite.