Multi-walled carbon nanotubes intertwined with porous Co₃O₄ nanoflakes (Co₃O₄/MWNT) have been hydrothermally synthesized to form a three dimensional network with superior electrical and ionic conductivity and tested as an anode material for lithium-ion batteries (LIBs). The electrochemical measurements on the Co₃O₄/MWNT composites demonstrated a reversible capacity of 708 mA h g⁻¹ after 100 cycles at a current density of 100 mA g⁻¹ and discharge capacities of 773, 805, 698, and 491 mA h g⁻¹ at current densities of 100, 200, 400, and 800 mA g⁻¹, respectively. The superior cycling and rate performances were attributed to the formed network structure, in which the entanglement and flexibility of MWNTs buffered the volume change of Co₃O₄ during the charge–discharge process and improved the electrical conductivity of the electrode.