Hollow LiNi0.8Co0.1Mn0.1O2-MgO coaxial fibers were prepared by employing the sol-gel proces combined with the coaxial electrospinning technique. The hollow coaxial fibers had a shell thickness of 30-60 nm and wall thicknesses of 300-500 nm. The polyvinyl pyrrolidone (PVP) had an important role in the formation of hollow structure. The electrochemical properties of hollow LiNi0.8Co0.1Mn0.1O2-MgO coaxial fibers were investigated by charge-discharge experiments. The hollow coaxial fibers as electrode materials showed a high discharge capacity and excellent cycle stability.