A novel Co3O4/N-doped porous carbon hybrid with dodecahedrons structure was synthesized by a facile, two-step, thermal transformation of a cobalt-based zeolitic imidazolate framework. Well-dispersed Co3O4 nanoparticles were embedded in nitrogen-doped porous carbon networks, forming a unique nanopolyhedron. When tested as anode material for lithium-ion batteries, the hybrid exhibited superior electrochemical performance, including excellent rate capability of 560mAhg−1 at 10Ag−1 which is close to 46% of the rate capacity at 100mAg−1, outstanding cycling stability with 91.7% capacity retention of the second cycle after 110 cycles, and considerably large discharge capacity of 1730 mAhg−1 at 100mAg−1. Moreover, the hybrid also showed enhanced electrocatalytic activity for electrochemical oxygen evolution from water splitting.