In this work, an inorganic hexagonal boron nitride (h-BN) dispersed vinyl (PVDF) and acrylic (PMMA) polymer blends were synthesized and its structure–property relationships were investigated. The structural identification by X-ray diffraction pattern confirms the semi-crystalline property of the h-BN dispersed blends. The internal morphology and topography details of the blends were studied by transmission electron (TEM) and atomic force microscopy (AFM). The chemical functionality of the polymer blends are changing after the dispersion of h-BN as confirmed from the IR spectrum analysis. The molecular interaction between PVDF, PMMA and h-BN is highly enhanced for 2 wt% loadings of h-BN. The dielectric constant (ε) as a function of frequency and temperature showed that there is a consistent increase in the value of ε at low frequency and high temperature for increasing loadings of h-BN and also a relatively low dissipation factor (tan δ) was obtained. The thermal stability was analyzed by TGA which is showing the enhanced thermal stability of blends as the h-BN wt% increases. The major interest of this study is to improve the dielectric and thermal properties of polymer blends for efficient electronic device applications. © 2019, Springer Science+Business Media, LLC, part of Springer Nature.