In today’s contemporary civilization, there is a growing need for clean energy focused on preserving the environment; thus, dielectric capacitors are crucial equipment in energy conversion. On the other hand, the energy storage performance of commercial BOPP (Biaxially Oriented Polypropylene) dielectric capacitors is relatively poor; hence, enhancing their performance has drawn the attention of an increasing number of researchers. This study used heat treatment to boost the performance of the composite made from PMAA and PVDF, combined in various ratios with good compatibility. The impacts of varying percentages of PMMA-doped PMMA/PVDF mixes and heat treatment at varying temperatures were systematically explored for their influence on the attributes of the blends. After some time, the blended composite’s breakdown strength improves from 389 kV/mm to 729.42 kV/mm at a processing temperature of 120 °C. Consequently, the energy storage density is 21.12 J/cm3, and the discharge efficiency is 64.8%. The performance has been significantly enhanced compared to PVDF in its purest state. This work offers a helpful technique for designing polymers that perform well as energy storage materials.