Carbon nanotubes when added to polymer matrices can generate significant changes in the properties of these materials. CNT can be added to broaden the application of the biopolymers, such as poly(3-hydroxybutyrate-co-3-hydroxyvalerate), PHBV. The addition of 1 and 2 wt% CNT by extrusion and later film production by compression improved the electrical and mechanical properties, and crystallinity of PHBV nanocomposites. These results revealed a good interaction between matrix and nanofiller, and the formation of a conductive network responsible for an increase of 8 orders of magnitude in the electrical properties.