Composite materials hold significant promise for advancing renewable energy storage solutions and enhancing efficiency. This study investigates the impact of reduced graphene oxide (rGO) on the structural and dielectric properties of K0.5Na0.5NbO3 (KNN). The samples were synthesized using both electrospinning and conventional solid-state methods. X-ray diffraction analysis confirmed the formation of a well-crystallized perovskite phase structure, with the incorporation of rGO reducing the crystallite size from 42.57 nm to 31.80 nm, indicating structural modifications. Rietveld refinement further corroborated the crystal structures of the ceramics, with chi-square χ2 values of 2.28 and 1.76 for KNN and KNN/rGO, respectively. Field emission scanning electron microscopy (FE-SEM) analysis revealed large grains, suggesting enhanced crystallinity or material aggregation due to rGO. The particle size distribution analysis indicated average sizes of 163.62 nm for KNN and 183.51 nm for KNN/rGO. Dielectric studies, conducted as a function of temperature and frequency, exhibited phase transitions, with an increased dielectric constant (ɛr) reaching 23,769 for KNN/rGO compared to 7,600 for KNN at 550 °C in the low-frequency region. The impedance diagrams for KNN and KNN/rGO displayed a typical semicircle response, indicating the presence of a grain/bulk effect in the material. The findings presented here demonstrate that rGO significantly enhances the structural and dielectric properties of KNN, rendering it a promising candidate for advanced energy applications.