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High-capacity anode materials are widely studied for rechargeable batteries, which have the capability of storing more Li+ ions per formula. However, they normally experience large volume expansion and suffer inferior cycling stability. Herein, we propose pea-pod structured V2O3 yolk-shell microspheres@N, S co-doped carbon fiber network as an excellent anode material for lithium ion batteries. The prepared vanadium dioxide precursor is uniformly embedded into the carbon fibers by electrospinning treatment and further converted into V2O3 yolk-shell microspheres during the calcination process. The conductive carbon fiber framework which links V2O3 microspheres enhanced the electrical conductivity and structural stability significantly. Moreover, the co-doped N and S atoms derived from polymer could produce extrinsic defects, thereby improving Li+ diffusion and electrochemical active sites. When used as anodes for lithium ion batteries, the composite exhibits a high reversible capacity (793.7 mA h g−1 after 100 cycles at 100 mA g−1), excellent rate performance and cycle stability.