A Sn-based intermetallic compound (hollow Si–Ni–Sn nanospheres) with a porous and hollow microspheric structure was fabricated via a versatile template synthesis approach followed by an in situ chemical reaction, and directly used as an anode material for lithium-ion batteries (LIBs). The hollow Si–Ni–Sn nanosphere anode with a unique architecture exhibits high initial discharge capacity and excellent cycling stability. The reversible capacity of hollow Si–Ni–Sn nanospheres is 1065 mA h g⁻¹ and is maintained at 402 mA h g⁻¹ after 50 cycles, which is much higher than that of hollow SiO₂@Ni@SnO₂ nanospheres. The unique configuration of the Sn-based intermetallic compound presents a beneficial approach to create efficient and practical electrodes for energy storage applications.