Abstract：[Ni(CH3COO)2＋PVP]@[SnCl4＋PVP]@[Zn(CH3COO)2＋PVP]@[Ti(OC4H9)4＋CH3COOH＋PVP] precursor composite cables have been fabricated through modified electrospinning equipment via electrospinning technique. NiO@SnO2@Zn2TiO4@TiO2 coaxial tetralayered nanocables were obtained by calcination of the relevant precursor composite cables. The samples were characterized by thermogravimetric-differential thermal analysis (TG-DTA), X-ray diffractometry (XRD), fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Results showed that the samples are coaxial tetralayered nanocables. The core layer is NiO, and its diameter is ca. 35～55 nm. The second layer is SnO2, and its thickness is 30～50 nm. The third layer is Zn2TiO4, and its thickness is 25～40 nm. The outer layer is TiO2, and its thickness is 40～90 nm. Formation mechanism of coaxial tetralayered nanocables was discussed.