Herein, we present heterogeneous hollow multi-shelled structures (HoMSs) prepared by exploiting the properties of the metal-organic framework (MOFs) casing. Through accurately controlling the transformation of MOF layer into different heterogeneous casings, we can precisely design HoMSs of SnO2@Fe2O3(MOF) and SnO2@FeOx-C(MOF), which not only retain properties of the original SnO2-HoMSs, but also structural information from the MOFs. Tested as anode materials in LIB's SnO2@Fe2O3 (MOF)-HoMSs demonstrate superior lithium-storage capacity and cycling stability to the original SnO2-HoMSs, which can be attributed to the topological features from the MOF casing. Making a sharp contrast to the electrodes of SnO2@Fe2O3 (particle)-HoMSs fabricated by hydrothermal method, the capacity retention after 100 cycles for the SnO2@Fe2O3 (MOF)-HoMSs is about eight times higher than that of the SnO2@Fe2O3 (particle)-HoMS.