Amorphous red phosphorus/carbon nanotubes (ARPC) composites are prepared by planetary ball-milling technique with the pre-milling red phosphorus processes, consisting of uniformly distributing amorphous red phosphorus embedding in a three-dimensional conductive scaffold of interconnected carbon nanotubes (CNTs). Combining the three-dimensional conductive network with the amorphous red phosphorus can not only alleviate the volumetric change in the charging/discharging processes, but also provide conductive network for electron transport and dramatically improve the specific capacity, cycling stability and rate capability of the composite electrode. The ARPC composites deliver a high initial charge capacity of 2133.4 mAh g−1 at a current density of 0.05 C and maintain a reversible capacity of 998.5 mAh g−1 with a high Coulombic efficiency of approximately 99% after 50 cycles. Meanwhile, the composite can maintain high specific capacities of 1993.8 mAh g−1, 1896.9 mAh g−1, 1546.8 mAh g−1 and 816.6 mAh g−1 at 0.01 C, 0.05 C, 0.1 C and 0.5 C, respectively. Compared with that of the ball-milled amorphous red phosphorus with or without CNTs, the pre-milled ARPC composites show much better electrochemical performances.