Complex nano-perovskite materials have recently gained attention as promising electrode materials for supercapacitors due to their high capacitances. The crystalline structure, dielectric properties, and electrochemical properties of LiZn0.5Mn0.5Ti3-xCexO8 (x = 0, 0.05, 0.1, & 0.15) pear-shaped nanoceramics, which were prepared through sol–gel reactions and sintered at 800 °C for 3 h, were explored. The XRD proves the well-crystalline structure for the prepared nanoceramic with the diffraction peaks corresponding to the cubic LiZnTi3O8 phase, the doped samples appearing with new peaks are matched to the cubic CeO2 phase. The impact of the Ce3+ ratio in the Li2Zn0.5Mn0.5Ti3O8 pear-shaped nanostructure on the dielectric properties of the nanoceramics is apparent, as the conductivity increases with increasing frequency and temperature. The electrochemical attitude can be ascribed to the LiZn0.5Mn0.5Ti3O8 pear-shaped nanostructure under the effect of Ce3+ ions producing continuous internal rearrangement. The capacitance values for Li2Zn0.5Mn0.5Ti3O8 doped with different ratios (3, 5, 10, 15%) Ce3+ are changed from 41.58 to 38.28 F.g-1, at scan rate (10) mVs-1. High electrocatalytic properties of the LiZn0.5Mn0.5Ti3-xCexO8 nanoceramics is approved using cyclic voltammetry, and electrochemical impedance spectroscopy. Furthermore, the Electrochemical analysis indicates that LiZn0.5Mn0.5Ti3-xCexO8 nanoceramics promising for supercapacitors applications.