In this study, VO 2 (B) nanorods were successfully synthesized using a simple hydrothermal route, in which templates or catalysts were absent. The synthesized VO 2 (B) nanorods are highly crystalline and have a rectangular cross-section. Following this, a possible model, reacting-exfoliating-recrystallizing, was proposed for the formation of VO 2 (B) nanorods. A lithium battery using VO 2 (B) nanorods as the active material of the positive electrode exhibits a high initial discharge capacity of 605mAhg −1 , revealing the formation of Li 1.82 VO 2 . Such a high degree of electrochemical performance is attributed to the intrinsic properties of crystalline VO 2 (B) nanorods.