Glass-like Si-O-C composites have recently attracted considerable attention because of their potential as high capacity anode for rechargeable lithium ion batteries. However, the existence of Si-C bonds in Si-O-C phase restricts in a certain degree the electrochemical activity of silicon. Here, we demonstrate the synthesis and electrochemical performance of SiOx-C dual-phase glass consisting of amorphous SiOx and free carbon phases and without Si-C bonds in SiOx phase. Dual-phase glass synthesis is achieved through a simple sol gel route. The SiOx-C dual-phase glass electrode delivers high reversible capacity of 840 mAh g(-1) for 100 cycles and exhibits excellent rate-capability. The superior electrochemical properties can be attributed to the unique dual-phase glass structure that the amorphous SiOx phase well-disperses and dense-contacts with free carbon component at nanoscale level. The SiOx phase with a lower O/Si ratio contributes the high reversible capacity while the well-contacted free carbon provides a good electronic conductivity for electrode reaction. In addition, the free carbon component can alleviate the volume change of SiOx component during discharge/charge process, which ensures an enhanced structural stability and an excellent cycling performance. (C) 2014 Elsevier B.V. All rights reserved.