We report, for the first time, a single step synthesis process of Li3Co2SbO6 in air medium using the solid state reaction route. The structural analysis confirmed single phase layered crystal structure comprising 2D diffusion path along a-axis and b-axis. The Rietveld refinement of Li3Co2SbO6 yielded monoclinic crystal structure with C2/m space group having cell parameters, a = 5.216 A°, b = 8.989 A° and c = 5.171 A° with Li/Co mixed occupancy. The TEM analysis corroborated the layered structure which is consistent with x-ray analysis. Raman and FTIR analysis confirmed the presence of -CoO6 and -SbO6 octahedra in Li3Co2SbO6 with edge shared arrangement to form a layered stack comprising tunnel type pathway for Li+ ion transport. The estimated electrical conductivity of Li3Co2SbO6 is found to be ∼6.9 × 10−8 Scm−1 with a band gap ∼ 3.5 eV that suggests poor electronic transport for storage cells. This was observed in the electrochemical response of the Li || LiPF6(EC/EMC) || Li3Co2SbO6 cell. The 1st discharge capacity of Li3Co2SbO6 has been found to be a meagre 45 mAhg−1. Despite lower reversible capacity due to poor electrical transport, stable coulombic efficency observed up to 100 cycles suggest the feasibility of improvements in the electrical and charge transport properties.