One-dimensional (1D) nanorods of LiV3O8 single crystals have been fabricated by using well-defined home-made VO2 (B) nanorods as the vanadium resource, combined with a convenient solid-state reaction. The as-obtained LiV3O8 nanorods were characterized by XRD, TEM and SEM, indicating this material was highly crystalline and a single phase. The electrochemical performance of LiV3O8 nanorods as the positive electrode material for rechargeable lithium batteries was investigated, which demonstrated that as-prepared LiV3O8 nanorods exhibited as high as 348mAhg−1 discharge capacity in first cycle at 20mAg−1 current density, and still remained at 303mAhg−1 at 50mAg−1 afterwards; moreover, until 50 cycles, they kept 315mAhg−1, recorded at 50mAg−1. All these results imply that single-crystalline 1D nanorods of LiV3O8 are promising cathode material for rechargeable lithium batteries.