With the proliferation of electronic gadgets and the internet of things comes a great need for lightweight, affordable, sustainable, and long-lasting power devices to combat the depletion of fossil fuel energy and the pollution produced by chemical energy storage. The use of high-energy-density polymer/ceramic composites is generating more curiosity for future technologies, and they require a high breakdown strength and dielectric constant. Interface polarization and electric percolation are responsible for the high dielectric constant. To create composite dielectrics, high-conductivity ceramic particles are combined with polymers to increase the dielectric constant. In this work, ternary nanocomposites with better dielectric characteristics are created using a nanohybrid filler of V₂C Mxene-ZnO in a polypyrrole (PPy) matrix. Then, the bonding and the non-uniform distribution of charges in the ceramic/ceramic interface zone are investigated using quantum mechanical calculations. This non-uniform distribution of charges is intended to improve the ceramic/ceramic interface's dipole polarization (dielectric response). The interfacial chemical bond formation can also improve the structural stability of the hybrid filler and, consequently, of the composite films. To comprehend the electron-transfer process, the density of state and electron localization function of the PPy with hybrid fillers are also studied. The polymer nanocomposite is anticipated to provide a suitable dielectric response for energy storage applications.