Constructing hollow structure and nano-sized SnO2 particles are two normal strategies to improve lithium storage performance of SnO2-based electrode. But it is still challengeable to fabricate ultrasmall SnO2 embedded in carbon hollow sphere in a controllable way. Herein, we have synthesized a kind of SnO2@carbon hollow sphere via a confined Friedel-Crafts crosslinking of a novel metal-organic compound (triphenyltin chloride, named Sn-Ph) on the surface of SiO2 template. The as-prepared SnO2@carbon hollow sphere has 10 nm-sized SnO2 particles embedded in amorphous carbon wall. Furthermore, 100, 200 and 400 nm-sized SnO2@carbon hollow spheres can be obtained by regulating the size of SiO2 template. When they are applied in lithium-ion batteries, the carbon structure can act as barriers to protect SnO2 particles from pulverization, and hollow core stores electrolyte and very small SnO2 particles of 10 nm shorten the diffusion distance of lithium ions. Thus, SnO2@carbon hollow sphere presents superior electrochemical performance. The first discharge and charge capacities reach 1378.5 and 507.3 mAh g (1) respectively, and 100 cycles later, its capacity remains 501.2 mAh g (1), indicating a capacity retention of 98.8% (C-100th/C-2nd). (C) 2018 Elsevier B.V. All rights reserved.