SnO2-C composite fibers with excellent electrochemical performance were successfully synthesized by using tin(II)2-ethylhexanoate as starting material through electrospinning technique and subsequent calcination in inert atmosphere. The experimental results of X-ray diffraction (XRD), Raman spectroscope, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), scanning electron microscope (SEM) and transmission electron microscope (TEM) show that SnO2-C composite fibers with diameters of 100-300 nm have amorphous structure and carbon content of ~38%. The electrochemical test results show that SnO2-C composite fibers exhibit initial discharge specific capacity, charge specific capacity and coulombic efficiency of 1370.1 mAh/g, 757.5 mAh/g and 55.28%, respectively, at current density of 50 mA/g. After 80 cycles at current density of 50 mA/g, the specific capacity of SnO2-C composite fibers remains at 611.6 mAh/g without apparent capacity reduction. Their high specific capacity and excellent cyclic performance are attributed to their one dimensional (1D) structure with homogeneous distribution of SnO2.