Hollow nanospheres of Sn–Sb–Cu alloy composites have been successfully synthesized via co-reduction of metal chlorides in aqueous alkaline solution without using any surfactants or solid templates. A bubble assisted growth mechanism is proposed to account for the formation of the hollow nanostructures. The concentration of the reactants kinetically controls the nucleation rate of the alloy nuclei, making for the formation of the hollow nanospheres. Compared with the alloy nanoparticles, the hollow spheres exhibit relatively high electrochemical capacity and good cyclic retention when used as anode materials for lithium-ion batteries. The bubble assisted synthesis method can be readily explored for fabricating hollow nanostructure of other alloy system for functional material applications.