In this work, uniform SnO2 hollow nanospheres with large void space have been synthesized by a modified facile method. The void space can be easily controlled by varying the reaction time. The formation of interior void space is based on an inside-out Ostwald ripening mechanism. More importantly, this facile one-pot process can be extended to fabricate rattle-type hollow structures using α-Fe2O3@SnO2 as an example. Furthermore, the electrochemical lithium storage properties have been investigated. It is found that α-Fe2O3@SnO 2 nanorattles manifest a much lower initial irreversible loss and higher reversible capacity compared to SnO2 hollow spheres. This interesting finding supports a general hypothesis that a synergistic effect between functional core and shell materials can lead to improved lithium storage capabilities. © The Royal Society of Chemistry 2009.