Amorphous ZnSnO3-C hollow microcubes have been produced by calcination of the pre-synthesized ZnSn(OH)6 hollow microcubes in argon, followed by the surface decoration of carbon. The calcination temperature plays an important role in the phase and morphology of the obtained products. ZnSnO3-C hollow microcubes have an average edge length of about 1.0μm with the shell thickness of approximate 145nm. When adopted as the anode materials for lithium ion batteries, amorphous ZnSnO3-C hollow microcubes manifest greatly enhanced electrochemical properties compared to amorphous ZnSnO3 hollow and solid counterparts. After 50th cycles, a high reversible capacity of 703mA h g−1 can be obtained for amorphous ZnSnO3-C hollow microcubes at the current density of 100mAg−1. The superior lithium storage properties of ZnSnO3-C are due to its unique hollow structure with large specific surface area, the modification of carbon and the amorphous characteristic.