Porous carbon supported carbon nanotube@CoP (PC@CNT@CoP) with 3D polyhedron structure has been prepared by a modified phosphorization approach for lithium ion batteries with enhanced performance. As a result, PC@CNT@CoP electrode exhibits high initial discharge capacity of 2410.9 mAh/g at current density of 0.1 A/g in the first circle, and reversible charge capacity of 1187.5 mAh/g. After 50 circles, the discharge capacity is 951.6 mAh/g, indicating 85.1% capacitance remaining. Even the current density increased to 5 A/g, the electrode still possesses capacitance of 155.4 mAh/g, illustrating the excellent rate capability.