Boron was doped into lithium trivanadate through an aqueous reaction process followed by heating at 100°C. The B-LiV3O8 materials as a cathode in lithium batteries exhibits a specific discharge capacity of 269.4mAhg−1 at first cycle and remains 232.5mAhg−1 at cycle 100, at a current density of 150mAhg−1 in the voltage range of 1.8–4.0V. The B-LiV3O8 materials show excellent stability, with the retention of 86.30% after 100 cycles. These result values are higher than those previous reports indicating B-LiV3O8 prepared by our synthesis method is a promising candidate as cathode material for rechargeable lithium batteries. The enhanced discharge capacities and their stabilities indicate that boron atoms promote lithium transferring and intercalating/deintercalating during the electrochemical processes and improve the electrochemical performance of LiV3O8 cathode.