Ceramic filler modified polymer blends are more in demand due to their excellent compatibility, easy processing and cost‐effectiveness. In the present work, we modified Polymethyl methacrylate (PMMA)/Polystyrene (PS) blends using solution blending with untreated (UT) and DC glow discharge plasma‐treated (air plasma treated‐APT) potassium hexatitanate (K2Ti6O13). Chemical bonding of virgin and modified blends was confirmed by Fourier transform infrared spectrophotometer (FTIR). Decreased structural defects and imperfections of KTO were confirmed by Raman spectroscopy. Modified surface morphology and elemental analysis were detected by scanning electron microscopy (SEM) and energy‐dispersive X‐ray analysis (EDAX). The quantification of particle size distribution has been determined by Zetasizer. Increased degree of crystallinity and decreased average crystallite size after plasma treatment were determined by X‐ray diffraction. Increased dielectric constant from ~22–200 and decreased loss up to 0.7 were analyzed by impedance analyzer. Lee's disc probe was deployed to confirm the optimized thermal conductivity of the modified blend system. By Differential Scanning Calorimetry, glass transition temperature of modified polymer blends was investigated. The change in surface from hydrophobic to hydrophilic by plasma exposure was confirmed by surface goniometer. However, the enhanced dielectric performance of modified PMMA/PS/KTO polymer blends may be suitable for flexible energy storage devices and gadgets.