A series of morphology/component-controllable Sn-Sb micro/nano-structures are fabricated by a one-pot replacement reaction technique employing metallic Sn as both template and reducing agent. Typically, nanoscaled Sn as template and ethyl alcohol as solvent give the hollow structure, while micron-sized Sn as precursor and ethylene glycol as solvent produce the dendritic product. Other mixed structures are also obtained by this one-pot route. As anode materials for lithium-ion batteries, the hollow or dendritic Sn-Sb materials exhibit higher discharge capacities compared with the corresponding Sb samples as well as the Sn templates. Especially, for the Sn-Sb hollow spheres, a high discharge capacity of 820.7 mAh g−1 after first cycle and a reversible capacity of 751 mAh g−1 are achieved after 100 cycles at a current density of 100 mA g−1. Meanwhile, the hollow Sn-Sb structure delivers a specific capacity of 451.3 mA h g−1 at 500 mA g−1 after 150 cycles when used for sodium ion batteries. The superior electrochemical performance that are higher than many reported results can be attributed to the special morphology and structure, which can shorten the transportation distance of lithium/sodium ion and provide extra free space to buffer the volume expansion during the lithium/sodium insertion/extraction.