Hierarchical ZnO-SnO2 composite nanofibers have been prepared through the single-nozzle electrospinning technique and subsequent calcinations using polyvinyl pyrrolidone as the fiber template and N,N-dimethylformamide as the solvent. The structures and morphologies of the samples were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The mesoporous nanofibers are composed of homogeneous grain-like nanoparticles, and heterostructures are formed between ZnO and SnO2. When used as the anode of lithium ion batteries, the ZnO-SnO2 composite nanofibers show first discharge and charge capacities of 1795 and 1364 mA h g(-1) at a current density of 50 mA g(-1). A reversible capacity of 588 mA h g(-1) is obtained after 100 cycles. The ZnO-SnO2 composite nanofibers prepared by such a simple and cheap method are expected to have a potential application in energy storage.