Lithium cobalt oxide (LiCoO2) which is being widely used as cathode material in lithium-ion batteries is synthesized by a novel solution-combustion procedure. In this synthesis, a solution mixture of Co(NO3)2, Li2CO3 and diformyl hydrazine fuel is heated to ignite at 350°C. This is accompanied by decomposition of cobalt nitrate and lithium carbonate to form LiCoO2 within a few minutes, which is annealed at 850°C for 6h to obtain an ordered-crystalline layered compound. The powder X-ray diffraction pattern of the prepared LiCoO2 shows a hexagonal cell with a=2.81 and c=13.83Å. Electrodes made with LiCoO2, acetylene black and poly(vinyledene fluoride) yield a discharge capacity of ∼120mAhg−1 with good Faradaic efficiency over several charge–discharge cycles. Cyclic voltammetric and ac impedance data also corroborate the electrochemical activity of LiCoO2 synthesized in the present study.