AbstractAs the energy demand continuously increases, polymer‐based materials have attracted much attention for energy storage systems as dielectric capacitors due to their higher power density and charge–discharge rate than lithium‐ion batteries and supercapacitors. However, it is necessary to increase the energy density of dielectric capacitors. In this context, poly(vinylidene fluoride‐co‐hexafluoropropylene), PVDF‐HFP, matrix nanocomposites are produced by solution casting method reinforced with hexagonal boron nitride (hBN) nanoparticles and silane‐modified boron nitride nanosheets ‐BNNSs‐ (BNNS‐VTS) up to 10 wt.% filler content. The effects of filler content and surface modification of hBN/BNNSs on PVDF‐HFP matrix nanocomposites' microstructure, phase evolution, crystalization behavior, dielectric properties, and energy storage performance are discussed. 4% hBN/PVDF‐HFP nanocomposite demonstrates 641 MV·m−1 of breakdown strength and 23.2 J·cm−3 of discharged energy density due to hexagonal boron nitride's excellent electrical insulating behavior. The achieved values are 3.0 and 10.5 times superior to the values of the neat thin film, respectively, and they are noteworthy among hBN‐ or BNNS‐reinforced PVDF‐based nanocomposites, even in multi‐layered structures. Furthermore, 4% hBN/PVDF‐HFP presents a giant charge–discharge energy efficiency (92%). It is thus demonstrated that hBN/PVDF‐HFP nanocomposites hold a great potential to be used in energy storage applications as flexible and lightweight dielectric capacitors.Highlights PVDF‐HFP matrix nanocomposites for electrical energy storage as flexible dielectric capacitors hBN NPs and silane‐modified BNNSs are reinforced into the matrix by 0–10 wt.%. The effects of filler content and surface modification of hBN/BNNSs are discussed. 4% hBN loading results in 23.2 J·cm−3 energy density and 92% efficiency at 641 MV·m−1 breakdown strength. Those metrics are relatively high in hBN‐ or BNNS‐reinforced PVDF‐based nanocomposites.