Nanoscale polymer dielectric films are critical demanded by continuously integration and miniaturization of energy electronic devices. In this paper, PVDF films are fabricated by present developed HSCA-LBD method, and thus, the dielectric properties of PVDF films with nanoscale thickness are investigated in detail for the first time. The results show that the films with thickness lower than 100 nm present excellent dielectric performances, the effective dielectric constant is up to 15 with loss less than 0.1 in frequency range of 1K - 2 MHz. The breakdown field of them is up to 171 MV/m with the energy density up to 2 J/cm(3), which are in same level with those of reported PVDF films with thickness higher than 10 mm. Moreover, the mechanisms of dielectric behaviors are also discussed in detail. (C) 2017 Elsevier Ltd. All rights reserved.