Sn/carbon nanofibers with well dispersed Sn nanoparticles embedded in carbon nanofibers were fabricated by an electrospinning process. A SnO2 sol was used as the Sn precursor in order to improve the compatibility of tin/carbon composites and prevent Sn nanoparticles from severe agglomeration upon thermal treatment. When evaluated as a binder-free anode for lithium ion batteries, the Sn/carbon nanofibers deliver a high specific capacity of 583 mA h g(-1) after 100 cycles and good cycling performance with coulombic efficiency up to 99%. The high lithium storage capability is mainly attributed to the optimized structure features including the well dispersed tin nanoparticles, high porosity, and the cushion effect of the carbon nanofibers.