Double-shelled hollow tin dioxide/poly(ethyleneglycol dimethacrylate-co-methacrylic acid) (SnO₂/P(EGDMA-co-MAA)) microspheres were prepared by selective removal of silica inner core via etching with hydrofluoric acid from the corresponding SiO₂/SnO₂/P(EGDMA-co-MAA) tri-layer microspheres. These tri-layer microspheres were synthesized by combination of modified St?ber method for silica inner core, hydrothermal technique for the sandwiched tin dioxide layer and distillation precipitation polymerization for coated P(EGDMA-co-MAA) shell-layer. The double-shelled hollow microspheres were utilized as anode materials for lithium-ion batteries, which had a significantly enhanced cycling performance than neat SnO₂ hollow spheres.