ZnO@CeO2 coaxial nanocables were successfully prepared by coaxial electrospinning, using cerous nitrate, zinc nitrate, polyvinyl pyrrolidone, N,N-dimethylformamide, glycerin and chloroform as starting materials. The samples were characterized by thermogravimetry and differential thermal analysis, X-ray diffractometry, scanning electron microscopy, transmission electron microscopy and energy dispersive spectroscopy techniques. The results show that ZnO@CeO2 coaxial nanocable has a diameter of ca. 90 nm, core diameter of ca. 60 nm and shell thickness of ca. 15 nm. The nanocable has a core of crystalline ZnO and a shell of crystalline CeO2. The length of the ZnO@CeO2 nanocables is greater than 300 mu m. The formation mechanism of the ZnO@CeO2 nanocables was preliminarily investigated.