Owing to its abundance and high theoretical capacity, phosphorus has attracted intense research interest as anode material for lithium-ion batteries. However, the adaption of phosphorus for batteries is still limited by its poor electrochemical performance, which is associated with its poor electronic conductivity and large volume change during charging and discharging. We herein report a facile and cost-effective method, which is based on high-energy mechanical milling, for the synthesis of phosphorus nanoparticles within carbon matrix as high-performance anode materials. Red phosphorus was readily transformed into orthorhombic black phosphorus at ambient temperature and pressure, forming phosphorus nanocrystals homogenously dispersed in carbon matrix. Such composites provide superior electrochemical performance, exhibiting reversible capacity of 1000 mA h g−1 after 300 cycles. Full cells based on such phosphorus-carbon composites against LiNi1/3Co1/3Mn1/3O2 cathode offer a capacity retention of 92% after 200 cycles at 0.5 C.