Ternary transition metal oxides are the important alternatives to commercial graphite for future lithium-ion batteries (LIBs). In this work, porous Co2FeO4 octahedral structures were synthesized by annealing the precursor from hydrothermal process, and the electrochemical properties of the samples as anode for LIBs were studied. Electrochemical measurements demonstrate that porous Co2FeO4 structures with octahedral shape display remarkably high discharge capacity, which is even slightly higher than the theoretical value of Co2FeO4. The specific capacity retention of Co2FeO4 porous structure annealed at 700°C reaches ca. 96.4% of that in the first cycle after 50 cycles. It is expected that the as-synthesized porous Co2FeO4 octahedrons can be a promising anode material for LIBs.