ABSTRACT Herein, we report an effective, fast and controllable electrochemical synthesis of layered structure LiNbO2 by electrolysis of solid Nb2O5 in molten LiF-LiCl salt. For the first time, the electrochemical performance of LiNbO2 as an anode for lithium ion battery is investigated. Such a material shows a high reversible capacity of ∼190mAhg−1 at 0.25C (1C=200mAg−1), superior rate capability (52mAhg−1 at 80C) and excellent long-term cycle stability (75mAhg−1 after 1000 cycles at 50C), due to the favorable kinetics benefiting from the high electronic conductivity and fast lithium diffusion in layered crystal structure of LiNbO2. It indicates that LiNbO2 is a promising anode candidate. Moreover, this work may provide a facile and controllable way to synthesize electrode materials for lithium ion batteries and other electrochemical energy storage applications.