Polyvinylidene fluoride (PVDF) and poly methyl methacrylate (PMMA) polymer blends were prepared by loading optimized quantity of attapulgite clay (AT) and hexagonal boron nitride (h-BN) nanopowder admixture. The crystalline phases were confirmed by X-ray diffraction patterns owing to the crystallinity of PVDF and h-BN. The shape and dimension of AT and h-BN fillers were confirmed by transmission electron microscope. The morphological changes were confirmed by scanning electron microscope, and the chemical composition of elements in the blends was confirmed by energy-dispersive spectroscopy. Frequency-dependent dielectric properties of the mixtures were explored as a function of temperature. The dielectric constant (εr) was improved (~ 6.87) when the AT and h-BN were loaded in an equal ratio (5:5 wt%). A low dissipation factor (tan δ) was obtained (~ 0.2) for the optimized loadings of AT and h-BN. Thermal stability of the blends was studied, and a delay in the degradation process at various steps was studied for AT/h-BN-incorporated PVDF/PMMA blends. The overall results suggest that the optimized loading of AT and h-BN significantly improved the dielectric and thermal properties of the PVDF/PMMA blends. © 2020, Springer Science+Business Media, LLC, part of Springer Nature.