A series of nanostructured silica–carbon composites containing different contents of SiO2 nanoparticles have been prepared from SiO2 nanoparticles-incorporated polyacrylonitrile (PAN) fibers via electrospinning and subsequent thermal treatment. The SiO2/C composites as negative material for lithium ion batteries benefit from both the high capacity of nano-SiO2 and the good performance of stable 3D nanostructured carbonaceous matrix. The nanostucture can effectively resist large volume changes and accelerate both the lithium ions diffusion and the electronic migration. The SiO2 content significantly affects on both the morphology and the electrochemical performance of the SiO2/C composites. It is found that the composite obtained from the SiO2/PAN fibers with 15wt% SiO2 exhibits a large capacity of 658mAhg−1 after 100 cycles at a current density of 50mAg−1 and retains 356mAhg−1 at 1000mAg−1, showing the best performance with high capacity, good rate capability and excellent cycling stability.