Carbon nanofiber (CNF)/unsaturated polyester resin (UPR) was prepared by a solvent evaporation method, and the temperature dependency of electrical conductivity was investigated. The CNF/UPR composites had quite a low percolation threshold due to CNF having a larger aspect ratio and being well dispersed in the UPR matrix. The positive temperature coefficient (PTC) was found in the CNF/UPR composites and it showed stronger effect around the percolation threshold. The electrical resistance of the CNF/UPR composites decreased and had lower temperature dependency with increasing numbers of thermal cycles.