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 1.0 μm with the shell thickness of approximate 145 nm. 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 703 mA h g⁻¹ can be obtained for amorphous ZnSnO₃-C hollow microcubes at the current density of 100 mA g⁻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.