CoV2O6/natural graphite electrode with sodium alginate binder is prepared, which shows excellent electrochemical performance as anode for Li-ion batteries. It exhibits initial discharge and charge capacity of 902 and 638 mAh g(-1) at a specific current of 110 mA g(-1). After 100 cycles, the discharge and charge capacity maintain of 669 and 665 mAh g(-1), respectively. The charge/discharge mechanism of CoV2O6 is also studied, suggesting a structure variation in discharging, which involves the initial formation of LiV2O5 and Co3V2O8, the subsequent transition from Co3V2O8 to LixV2O5 and CoO, and the later reduction of Co into Co. The structure variation of Co3V2O8 accompanies by an amorphization process, which maintains in the subsequent discharging and charging process. (C) 2015 Elsevier B.V. All rights reserved.