Sol-gel based electrospinning has been developed to synthesize phase pure LiCoO2 powders at relatively low temperature with excellent crystallinity and ultrafine particle size. Compared to LiCoO2 powders synthesized from regular sol-gel processes, the nanofiber derived powders possess high initial discharge capacity and good cyclic stability, and the retention of initial capacity is also much higher than bare LiCoO2 nanofibers reported in literature. With additional surface modification of La2O3 coating, the retention of initial capacity is increased to 91% at 30th cycle and 83% at 50th cycle without decreasing its initial capacity, making it attractive for Li-ion batteries. (C) 2012 Elsevier Ltd. All rights reserved.