High dielectric composites were prepared based on polyvinylidene fluoride (PVDF) and hybrids BaTiO3-carbon nanotubes (H-BT-CNTs) with a special structure. The hybrids that BT was a core and CNTs grew outside were fabricated by chemical vapor deposition. Due to the special structure, composite's dielectric permittivity reached 1777 at 100 Hz and 80 at 1 MHz, while loss tangent maintained as 6 at 100 Hz and 0.56 at 1 MHz, respectively. Moreover, dielectric permittivity and ac conductivity of composite were further enhanced after annealing process at moderate temperature. These improved properties were originated from the reformation of conductive network and BT-CNTs structure inside PVDF matrix.