To explore good anode materials of high safety, high reversible capacity, good cycling, and excellent rate capability, a Li3VO4 microbox with wall thickness of 40 nm was prepared by a one-pot and template-free in situ hydrothermal method. In addition, its composite with graphene nanosheets of about six layers of graphene was achieved. Both of them, especially the Li3VO4/graphene nanosheets composite, show superior electrochemical performance to the formerly reported vanadium-based anode materials. The composite shows a reversible capacity of 223 mAh g−1 even at 20C (1C = 400 mAh g−1). After 500 cycles at 10C there is no evident capacity fading.