Lanthanum-doped LiCoO2 composite cathode materials, containing 0.1–10mol% of La were synthesized by citric acid aided combustion technique. Thermal analyses showed that the sharp decomposition reaction for pristine LiCoO2 became sluggish upon addition of lanthanum. X-ray diffraction analyses of the composites revealed existence of minute quantities of lanthanum-rich perovskite phases—rhombohedral LaCoO3 ( R 3 ¯ ) and tetragonal La2Li0.5Co0.5O4 (14/mmm), along with rhombohedral LiCoO2 ( R 3 ¯ m ) . Electron microscopy showed a distinct grain growth with increasing La content. An increase of about two orders of magnitude in the electrical conductivity (1.09×10−3 Scm−1) was observed for 1.0mol% La-doped LiCoO2. An excellent cycling performance with capacity retention by a factor of ∼10 in comparison to the pristine LiCoO2 was observed for the composite cathode containing 5.0mol% La, when 2032 type coin cells were cycled at 5C rate. This has been ascribed to the structural stability induced by La doping and presence of the ion-conducting phase La2Li0.5Co0.5O4 which acts as a solid electrolyte for Li+ ions. A negligible growth of impedance upon repeated cycling has been observed. Cyclic voltammetry showed a remarkable improvement in reversibility and stability of the La-doped electrodes. These composite cathodes might be very useful for high rate power applications.