A novel Sb/C polyhedra composite is successfully fabricated by a galvanic replacement reaction technique using metal organic frameworks as templates. In this composite, the ultrasmall Sb nanoparticles with an average size of 15 nm are homogeneously encapsulated into the carbon matrixes, forming a hierarchical porous structure with nanosized building blocks. Used as an anode material for lithium ion batteries, this composite exhibits high lithium storage capacities, excellent rate capability and superior cycle stability, higher than many reported results. Notably, a discharge capacity of 565 mAh g−1 at a current density of 0.2 A g−1 is delivered after 100 repeated cycles. Even at a high current density of 1 A g−1, a discharge capacity of 400.5 mAh g−1 is also maintained after 500 cycles. Such superior cycling stability and rate discharge performance of the designed Sb/C composite can be attributed to the synergistic effect between Sb nanoparticles and the porous carbon matrixes.