Polymer-based composites act as film capacitors are an ideal candidate, but further applications are limited by the conflict between energy density and efficiency. Herein, a novel one-dimensional core–shell tubular structure of nanofillers is proposed, SiO2 surface-modified Ba0.6Sr0.4TiO3 nanotubes ([email protected]2 NTs) are prepared by improved electrospinning and then wet chemical method. Notably, both improved dielectric properties and enhanced breakdown strength could be obtained by incorporating moderate [email protected]2 NTs. Consequently, the 2 vol% [email protected]2 NT/PVDF composites achieve an ultra-high Ud (discharged energy density) of ~ 18.08 J/cm3,and it is quite larger than 11.25 J/cm3 of neat PVDF. More importantly, compared to pure PVDF (59.87%), an excellent efficiency of 70.06% is also maintained. This work opens up a novel and unique sight for the structural designing of inorganic nanofillers, which is the ideal strategy to obtain high-performance dielectric composites and related potential applications.