TiO2 can be integrated with antimony-doped tin oxide to obtain composite materials with high electroconductivity. Based on this, spherical TiO2@Sb-SnO2 (TSS) has been prepared by homogeneous precipitation combined with a high-temperature calcination process. The morphology, structure and composition of TSS were characterized by scanning electron microscope, Brunauer-Emmet-Teller surface area analyzer, X-ray diffractometer and transmission electron microscope with energy-dispersive X-ray spectrometer, respectively. Effects of dropping conditions, introducing sulfate, pH value, calcination temperature and holding time on the conductivity of TSS were investigated by measuring resistivity, Zeta potential and particle size, meanwhile the calcination action and conductive mechanism by thermogravimetric analysis, X-ray photoelectron spectroscopy and electron spin resonance. The results revealed that the core-shell structured TSS was formed, and the resistivity of composite powder was below 4.0 Omega cm under the optimum conditions. Our analysis indicates that the conductive channel mechanism is the main conductive mechanism of the as-prepared composite.