Si/Cu3Si@C composites encapsulated in CNTs network (SCC-CNTs) were synthesized via the combination of ball-milling and CVD methods. SCC-CNTs consist of conductive Cu3Si, amorphous carbon layer, cross-linked CNTs, and the etched pores, which can play the synergistic effects on the improvement of electronic conductivity and Li+ diffusion. The volume expansion of Si anode is also suppressed during the electrochemical process. The SCC-CNTs composites demonstrate a remarkably improved electrochemical performance compared with pure Si, which can deliver a discharge capacity of 2171 mAh·g-1 at 0.4 A·g-1 with ICE of 85.2％, and retain 1197 mAh· g-1 after 150 cycles. This work provides a facile approach to massively produce the high-performance Si-based anode materials for next-generation LIBs.