Cathodic corrosion, a green electrochemical method, has been employed to obtain Sb nanomaterials utilized as anode material for lithium-ion batteries and sodium-ion batteries. Interestingly, two different corrosion mechanisms are found, coming from the impact of electrolyte, resulting in the formation of hexagonal and amorphous Sb in aqueous and organic solution, respectively. With the help of water-soluble carboxymethyl cellulose binder and the electrolyte additive fluoroethylene carbonate, both hexagonal and amorphous Sb electrodes exhibit good cycling stability when utilized as anode materials for lithium-ion batteries and sodium-ion batteries. Additionally, both the hexagonal and amorphous Sb electrodes show very good rate capability in lithium-ion batteries. Even at high current density (2000 mA g−1), the hexagonal and amorphous Sb give reversible capacities of 422 and 379 mA h g−1, respectively. Surprisingly, when used as anode materials for sodium-ion batteries, the hexagonal Sb electrode exhibits a good rate performance of 632, 625, 569, 515 and 426 mA h g−1 at a current density of 100, 200, 500, 1000, and 2000 mA g−1, respectively. However, limited rate performance is observed from the amorphous Sb electrode in case of sodium-ion battery due to the large impedance.