We have studied the preparation of LiCoO2 powder using the metallo-organic decomposition (MOD) route in air. Cobalt and lithium 2-ethylhexanoate were obtained from hydroxides and 2-ethylhexanoic acid. TG/DTA and XRD techniques were used to study the steps of formation of well-organized LiCoO2 (R-3m). The MOD route produced LiCoO2 (R-3m) at 700°C with specific surface area 1.7m2 g−1 and grain size distribution d 50=24μm. The electrochemical response of MOD LiCoO2 powder was tested by cyclic voltammetry and discharge/charge cycles in a composite electrode. The MOD method yields LiCoO2 agglomerated particles with size distribution and porosity that facilitate lithium diffusion in the composite electrode.