Three-dimensional (3D) architectures of layered LiCoO2 fibers 60-80 nm in diameter have been prepared by an electrospinning method for rechargeable lithium-ion batteries. To resolve the instability of a 3D structure induced by lithium intercalation and deintercalation, a lithium phosphorous oxynitride (LiPON) layer was coated into the 3D structure. The 3D electrode of electrospun LiCoO2 fibers with a LiPON layer had a better rate capability and higher reversibility as compared with the electrospun LiCoO2 fibers without a LiPON layer, indicating the effectiveness of the LiPON layer for application of LiCoO2 fibers in rechargeable lithium-ion batteries.