Lithium cobalt oxide (LiCoO{sub 2}) is known to be a good cathode material for high voltage (4V) rechargeable Li-ion batteries. New chemical routes based on aqueous solution chemistry have been developed to synthesize molecularly mixed precursors that transform to form LiCoO{sub 2} at temperatures as low as 400{degrees}C. The resultant oxide powders are nanocrystalline ({approx} 20-40 nm) and exhibit unique morphologies and microstructures depending on the molecular environment of the ions in solution. Cathodes fabricated from the oxide powders and tested in {open_quote}hockey-puck{close_quote} test cells exhibited specific capacities of about 135 mAh/g with a reversible range close to 0.5 Li ions. Results of the phase evolution and microstructural analysis are discussed in relation to the electrochemical performance of the cathodes.