Under optimized synthesis conditions, very large area uniform SnO2 nanofibers consisting of orderly bonded nanoparticles have been obtained for the first time by thermal pyrolysis and oxidization of electrospun tin(II)2-ethylhexanoate/polyacrylonitrile (PAN) polymer nanofibers in air. The structure and morphology were elaborated by X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The SnO2 nanofibers delivered a reversible capacity of 446mAhg−1 after 50 cycles at the 100mAg−1 rate and excellent rate capability of 477.7mAhg−1 at 10.0C. Owing to the improved electrochemical performance, this electrospun SnO2 nanofiber could be one of the most promising candidate anode materials for the lithium-ion battery.