Poly(vinylidene fluoride) (PVDF) / multi-walled carbon nanotube (MWNT) thermoplastic composites was melt compounded in an internal mixer. The percolation level for this system in electrical conductivity clearly occured between 2 and 2.5 wt%. PVDF/MWNT thermoplastic composites exhibited an increased crystallization temperature with the loading level, at 10 wt% loading by ca. 6. In addition, they presented a shoulder posterior to the main melting peak and an increased endpoint of the peak. In the Wide Angle X-ray Diffraction (WAXD) patterns, the incorporation of MWNT produced a larger shoulder at 2θ =20.7° with increasing the loading level, corresponding to the β-form crystal of PVDF.