Red phosphorus for lithium-ion batteries (LIBs) is considered to be promising electrode material due to the high theoretical capacity and moderate working potential. However, the enormous volumetric expansion and intrinsic poor electrical conductivity result in poor interfacial stability and sluggish reaction kinetics. Herein, different functional conductive polymers are introduced to modify the interface, aiming to improve the interfacial compatibility and mechanical stability between red phosphorus and matrix materials. The Cobalt polyphthalocyanine (CoPPc)/polydopamine (PD) hybrid interface not only facilitates electron transfer within the system, but also accommodate the volume expansion of red phosphorus. Consequently, the novel P/CoPPc@PD anode achieves a stable specific capacity of 650 mAh g−1 after 580 cycles at 200 mA g−1, and a discharge capacity of 385 mAh g−1 at 5.0 A g−1 even after 10,000 cycles, demonstrating outstanding long-term cycling stability and rate performance.