The effect of surface free energy on the positive temperature coefficient (PTC) of carbon black/thermoplastic resin composites was investigated. The thermoplastic resins such as EVA, LDPE, LLDPE and HDPE were used with the addition of 30 wt.% of the carbon black. The surface free energy of the composites was studied in the context of two-liquid contact angle measurements, i.e., deionized water and diiodomethane. It was observed that the resistivity on PTC composites Was greatly increased near the crystalline melting temperature, due to the thermal expansion of polymeric matrix. From the experimental results, it was proposed that the decrease of surface free energy induced by interactions between carbon black surfaces and polymer chains is an important factor to the fabrication of a PTC composite made of carbon black and polymeric matrix.