In an effort to increase and sustain the reversible capacity of LiCoO2 on cycling, LiCoO2 is prepared by using the molten-salt of the eutectic LiNO3–LiCl at temperatures 650–850°C with or without KOH as an oxidizing flux. The compounds are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), chemical analysis, surface area and density techniques. Cathodic behaviour was examined by cyclic voltammetry (CV) and charge–discharge cycling. The 850°C-synthesized LiCoO2, which has excess lithium incorporated in to it, shows a reversible capacity, with ∼98% coulombic efficiency, of 167 (±2) mAhg−1 at a specific current of 30mAg−1 in the range 2.5–4.4V up to 80 cycles with no capacity-fading. When cycled to a higher cut-off voltage (4.5V), a capacity of 192 (±2) mAhg−1 versus Li is obtained at the fifth cycle, but capacity-fading is observed, viz., ∼6% after 60 cycles. On the basis of the CV and capacity–voltage profiles, this is attributed to the non-suppression of the hexagonal (H1)↔(H1-3) structural transition. A similar capacity-fading, i.e., ∼5–6%, during 5–40 cycles, is also observed in the LiCoO2 prepared at 650 and 750°C when cycled up to only 4.3V and this is ascribed to the non-suppression of the H1↔M↔H1 phase transitions (M=monoclinic).