We have fabricated a micron-sized LiCoO2/LiCo0.99Ti0.01O2 composite successfully by solid-phase synthesis, its core-shell structure has been proved by SEM and XPS observation. Electrochemical examinations show that comparing with LiCoO2 and LiCo0.99Ti0.01O2, the obtained LiCoO2/LiCo0.99Ti0.01O2 composite presents greatly enhanced cycling stability as well as rate capability. In addition, DSC measurement indicates that LiCoO2/LiCo0.99Ti0.01O2 has a better thermal safety than LiCoO2. It is considered that all the improvement should be explained by the particular core-shell morphology of the LiCoO2/LiCo0.99Ti0.01O2 sample.