In this study, VO2 (B) nanorods were successfully synthesized using a simple hydrothermal route, in which templates or catalysts were absent. The synthesized VO2 (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 VO2 (B) nanorods. A lithium battery using VO2 (B) nanorods as the active material of the positive electrode exhibits a high initial discharge capacity of 605 mAh g(-1), revealing the formation of Li1.82VO2. Such a high degree of electrochemical performance is attributed to the intrinsic properties of crystalline VO2 (B) nanorods. (C) 2010 Elsevier B.V. All rights reserved.