A versatile one-step method for the general synthesis of metal oxide hollow nanostructures is demonstrated. This method involves the controlled deposition of metal oxides on shaped α-Fe2O3 crystals which are simultaneously dissolved. A variety of uniform SnO2 hollow nanostructures, such as nanococoons, nanoboxes, hollow nanorings, and nanospheres, can be readily generated. The method is also applicable to the synthesis of shaped TiO2 hollow nanostructures. As a demonstration of the potential applications of these hollow nanostructures, the lithium storage capability of SnO2 hollow structures is investigated. The results show that such derived SnO2 hollow structures exhibit stable capacity retention of 600–700 mAh g−1 for 50 cycles at a 0.2 C rate and good rate capability at 0.5–1 C, perhaps benefiting from the unique structural characteristics.