Metal-organic frameworks can provide excellent templates for the preparation of nanomaterials for green energy storage. However, it is still a formidable challenge for the synthesis of MOF-templated Sn-based nanomaterials with controllable morphologies and structures. Here, Sn-based MOFs with different morphologies are synthesized by a facial and controllable method, then SnO/C polyhedrons with shapes of cube and stellated octahedron are obtained using the Sn-based MOFs as template by further heat treatment, respectively. Benefited from the composite structures, the SnO/C polyhedrons exhibit excellent electrochemical performances in lithium storage. A high reversible capacity of 950 mA h g−1 is obtained at a current density of 50 mA g−1 after 100 cycles, together with superior cyclic stability and remarkable rate capacity. This paper provides an effective route to prepare high-performance Sn-based anode materials from the morphology-controlled MOFs for lithium-ion batteries.