Uniform Sn/C hybrid core/shell nanocomposites were synthesized by a combination of electrospinning and subsequent thermal treatment in a reducing atmosphere. The particular three-dimensional architecture, consisting of a Sn@C nanoparticle core and porous hollow carbon nanofiber shell, is characterized by many micro/nanochannels, enhanced mechanical support from the three-dimensional hollow carbon shell, and the abundant porous carbon matrix. The as-prepared Sn/C core/shell nanomaterials exhibit excellent electrochemical performance. They display a reversible capacity of 546.7mAhg-1 up to 100 cycles at the current density of 40mAg-1 and good rate capability of 181.8mAhg-1 at 4000mAg-1. These results indicate that the composite could be a promising anode candidate for lithium ion batteries.