Highly porous Ni3Sn2 microcages composed of tiny nanoparticles were synthesized by a facile template-free solvothermal method (based on Ostwald ripening and etching mechanism) for use as anode materials for high-capacity and high-rate-capability Li-ion and Na-ion batteries. The Ni3Sn2 porous microcages exhibit highly stable and substantial discharge capacities of the amount to 700 mA h g–1 after 400 cycles at 0.2C and 530 mA h g–1 after 1000 cycles at 1C for Li-ion battery anode. For Na-ions storage performance, a reversible capacity of approximate 270 mA h g–1 is stably maintained at 1C during the first 300 cycles.