Hierarchical porous MWCNTs/ZnO (MCZO) nanocomposites are prepared using a Zn-based metal organic framework (MOF) template. In these MCZO nanocomposites, the ZnO polyhedrons (~600nm) with MWCNTs inserted consist of nanosized building blocks (~10nm) and possess a large specific surface area of 94.13m2 g−1, robust pore structure as well as highly uniform morphology. When tested as anode material for lithium-ion batteries (LIBs), as-synthesized nanocomposites manifest enhanced lithium storage performance with high reversible capacity (419.8mAhg−1 after 100cycles at a current density of 200mAg−1), good rate capability and cycling stability, which could be attributed to the synergetic effect between the MWCNTs and the stable porous ZnO polyhedron structure.