A novel way for the synthesis of core/shell structures composed of tin oxide nanoparticles confined in mesoporous hollow carbon spheres (SnO2@MHCS) is newly reported. The materials which have a uniform size distribution, good structural stability and large surface area show superior cycling performance and are suitable for high-power anodes. Core/shell structured SnO2@MHCS takes advantage of the virtues of SnO2 and porous carbon in lithium-ion battery. This structure provides a rapid lithium transport pathway and boasts a highly reversible capacity. When the SnO2/C ratio is 78.6/21.4 (w/w), the surface area of SnO2@MHCS is 183 m2 g−1 and specific capacity value is 450 mAh g−1 at 1/5 C after 50 cycles. The SnO2@MHCS materials have large potential in next-generation lithium-ion batteries.