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Polymethyl methacrylate (PMMA)-coated hollow Sn–Co nanospheres (Sn–Co@PMMA) with superior electrochemical performance had been synthesized via a facile galvanic replacement method followed by an in situ emulsion polymerization route. The properties were investigated in detail and results show that the hollow Sn–Co nanospheres were evenly coated with PMMA. Benefiting from the protection of the PMMA layers, the hollow Sn–Co@PMMA nanocomposite is capable of retaining a high capacity of 590 mAh g −1 after 100 cycles with a coulomb efficiency above 98%, revealing better electrochemical properties compared with hollow Sn–Co anodes. The PMMA coating could help accommodate the mechanical strain caused by volume expansion and stabilize the solid electrolyte interphase (SEI) film formed on the electrode. Such a facile process could be further extended to other anode materials for lithium-ion batteries. [ABSTRACT FROM AUTHOR]