Abstract We reported a novel high voltage cathode having layered structure and manifold improvement (144%) in electrochemical performance on carbon coating Li3Co2SbO6. The carbon-coated Li3Co2SbO6 has been prepared using a high temperature solid-state method in an air medium with appropriate stoichiometry of the oxide and carbon source (sucrose). The x-ray diffraction and high-resolution transmission electron microscopy results have confirmed homogeneous carbon coating on oxide (Li3Co2SbO6) surface without disturbing phase, structure and morphology. The immediate effect of carbon coating resulted in electrical conductivity enhancement of the carbon coated Li3Co2SbO6 by four order of magnitudes ∼2.79 × 10−4 Scm−1 at room temperature vis-a-vis pristine Li3Co2SbO6. The electrochemical performance of the carbon coated Li3Co2SbO6 has shown sustainable improvement indicating redox activity by more than one Li+ transaction. The carbon coated Li3Co2SbO6 cathode exhibited an initial discharge capacity of 110 mAhg−1 compared to 45 mAhg−1 for its pristine counterpart. The improvement in electrochemical capacity on carbon coating, as reported in this work, is the highest ever compared to prior literature reports on Li3Co2SbO6.