Dispersion and electrical properties of fluorinated carbon black-filled poly(vinylidene fluoride) (PVDF) composites were studied as a function of the fluorine content. It was found that with increasing the fluorine content carbon particles tend to stick together to form large aggregates. The percolation concentration increases to a high concentration, whereas the percolation process becomes gradual. The temperature dependence of resistivity measurements show that the fluorinated carbon black-filled PVDF composites exhibit a high PTC intensity and a low NTC effect. These phenomena were discussed in terms of thermodynamic interactions between fluorinated carbon and the PVDF matrix. The dielectric behavior was also investigated in this study.