Undoped carbon nanotubes (CNTs) and N‐CNTs are synthesized by chemical vapor deposition using Fe catalyst, and then melt‐mixed in an APAM mixer with polyvinylidene fluoride (PVDF) to prepare the nanocomposites. The morphology, crystallinity, aspect ratio, nitrogen content, and nitrogen bonding type of CNTs, and the broadband dielectric properties of undoped CNT/PVDF and N‐CNT/PVDF nanocomposites are analyzed. The results show that while undoped CNTs present a crystalline structure with open channels, doping with nitrogen results in CNTs with a bamboo‐like configuration, inferior crystallinity, smaller length, and larger diameter. The N‐CNT/PVDF nanocomposites, thus, have a higher percolation threshold (≈ 3.5 wt%) compared to that of the undoped CNT/PVDF nanocomposites (≈ 0.5 wt%). Comparison of the broadband dielectric properties of the generated nanocomposites reveals that nitrogen doping improved the dielectric properties in the insulative region. This is ascribed to the role of nitrogen atoms and their sequent defects in the nanotubes, which act as scattering centers and provide additional polarization sites. For instance, 1.0 wt% N‐CNT/PVDF nanocomposites exhibit a real permittivity of ε′ = 22 and a dissipation factor of tan δ = 0.03 at 1 kHz, a combination superior to that of 0.5 wt% undoped CNT/PVDF nanocomposite with ε′ = 11.2 and tan δ = 3.8, and 1.0 wt% undoped CNT/PVDF nanocomposites with ε′ = 40 and tan δ = 1.4 × 105.