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The Li2MnO3-modified Li1.2NixCo0.1Mn0.9-xO2(x = 0.2, 0.45, 0.7) as cathode materials for lithium-ion batteries have been successfully synthesized by a simple electrospinning process. The structure, morphology and electrochemical performances of the resulting products are studied systematically. The as-prepared Li2MnO3-modified Li1.2NixCo0.1Mn0.9-xO2(x = 0.2, 0.45, 0.7) with a diameter of 200-300 nm has an initial discharge capacity of 168.740 mAh·g−1, coulombic efficiency of 99.6% and a reversible capacity as high as 139.016 mAh·g−1after 200 cycles at a current rate of 0.2 C. The excellent electrochemical performances of which are attributed to the stabilization of Li2MnO3structure, the role of Li2MnO3is contribute extra lithium to the reversible capacity and to facilitate Li+transport through the structure.