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SiO x has aroused great attractions as a promising substitute for the anode materials of high-performance lithium-ion batteries (LIBs) because of the high specific capacity and the longer cycle life as well as relatively low volume expansion compared to Si. However, the unstable structure and poor conductivity of the SiO x lead to unideal electrochemical properties in LIBs, and thus hindering the widespread application of the SiO x anode. Herein, a facile approach has been put forward to prepare the high-performance mesoporous structure SiO x /carbon (m-SiO x /C) composites by electrospinning technique and sintering processes. The spherical SiO x nanoparticles are well anchored on the carbon fibers, and the reserved space can accommodate large volume expansion of the SiO x materials. Besides, the fibrous carbon materials can significantly enhance the conductivity for the SiO x anodes. Therefore, the resultant m-SiO x /C composites exhibit high discharge specific capacity of 1434 mAh g−1 at 500 mA g−1 with 67.5% capacity retention after 500 cycles and the good rate properties of 410 mAh g−1 at 2000 mA g−1. In consequence, the reasonable structural design and innovative fabrication technique can facilitate the practical application for the m-SiO x /C composites and further promote the comprehensive electrochemical performance of LIBs. [ABSTRACT FROM AUTHOR]