Si@C@CNT@C composite is prepared by preliminary low-pressure forming Si@C and Si@C@CNT precursors from Si powder. After pyrolysis from glucose, acetylene and pitch, Si@C@CNT@C shows a spherical multi-phase composite structure. By using as lithium storage material, Si@C@CNT@C shows an initial discharge capacity of 620.5mAhg−1 with an initial coulombic efficiency of 82.2%. After 60 cycles, this spherical sample can maintain a reversible capacity of 563.5mAhg−1 at 100mAg−1, corresponding to a capacity retention of 90.8%. For comparison, the reversible capacities for Si powder, Si@C and Si@C@CNT are 10.9, 380.3 and 494.6mAhg−1, respectively. Even cycled at 400mAg−1, Si@C@CNT@C can deliver a reversible lithium storage capacity of 389.2mAhg−1. It indicates that spherical Si@C@CNT@C can be used as a high performance anode material for lithium-ion batteries.