A novel silicon-based glassy composite anode material with high initial coulombic efficiency and long cycling performance for lithium-ion batteries was synthesized by a wet mechanochemical reduction method. The in Situ formed Si particles with size of 5-10 nm were uniformly distributed in the glassy matrices formed by B(2)O(3) and P(2)O(5). The as-prepared composite electrode revealed an initial charge and discharge capacity of 432.7 and 514.4 mAh g(-1) respectively, with an initial coulombic efficiency of 84%. After 100 cycles, the reversible capacity retention rate was still up to 97%, meaning a favorable cycling stability. (C) 2010 Elsevier B.V. All rights reserved.