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Increasing the energy density of lithium-ion batteries (LIBs) can broaden their applications in energy storage but remains a formidable challenge. Herein, with polyacrylic acid (PAA) as phase separation agent, macroporous Co₂SnO₄ with hollow skeletons was prepared by sol-gel method combined with phase separation. As the anode of LIBs, the macroporous Co₂SnO₄ demonstrates high capacity retention (115.5% at 200 mA·g⁻¹ after 300 cycles), affording an ultrahigh specific capacity (921.8 mA h·g⁻¹ at 1 A·g⁻¹). The present contribution provides insight into engineering porous tin-based materials for energy storage.