Nano-sized SnO2 hollow spheres are facilely synthesized by sol–gel method using the SiO2 nanospheres as sacrificed templates, and their electrochemical properties are investigated as an anode application for lithium ion battery (LIB). The size of the hollow spheres is controlled by using different-sized templates. As-coated SnO2 shell is almost amorphous and transformed into a rutile phase after annealing at 600 °C. The size of the SnO2 hollow spheres ranges from 25 to 100 nm. The shell thickness is almost constant (∼5 nm) irrespective of the size of the hollow spheres. The hollow spheres showed the size dependent electrochemical properties, and the smallest SnO2 (25 nm) hollow sphere exhibited a high reversible capacity of 750 mAh g−1 as well as excellent cyclability.