The ceramic-polymer nanocomposites consisting of Ba0.6Sr0.4TiO3 nanofibers (BST60 NF) with a large aspect ratio prepared via electrospinning and employing surface hydroxylated as fillers and poly(vinylidene fluoride) (PVDF) as matrix have been fabricated by a solution casting method. The nanocomposites exhibit enhanced permittivity, reduced loss tangents and improved breakdown electric field strength at a low volume fraction of hydroxylated BST60 NF. The energy density of the nanocomposites is significantly enhanced, and the maximal energy density of 6.4 J/cm(3) is obtained in the composite material with 2.5 wt % hydroxylated BST60 NF, which is more than doubled as compared with the pure PVDF. Such significant enhancements result from combined effect of the large aspect ratio, the surface modification and the improved crystallinity of the nanocomposites induced by the hydroxylated BST60 NF. This work may provide a route for using the hydroxylated ceramic nanofibers to enhance the dielectric energy density in ceramic-polymer nanocomposites.