Lithium trivanadate (LiV3O8) powders are prepared by spray pyrolysis. The precursor powders of LiV3O8 obtained by spray pyrolysis have spherical and rod-like morphologies. The LiV3O8 powders post-treated at 300°C and 400°C also have spherical and rod-like morphologies. However, the LiV3O8 cathode powders post-treated at 500°C consist of only rod-like crystals. The crystalline structure of the precursor powders that were directly prepared by spray pyrolysis comprised of LiV3O8 layers along with a small amount of β-Li0.33V2O5 impurity. The peak due to β-Li0.33V2O5 persisted in the XRD spectrum even after post-treatment at 300°C. On the other hand, crystalline structures of the powders post-treated at 400°C and 500°C comprised pure LiV3O8 layers. The initial discharge capacities of the LiV3O8 cathode powders decrease from 344mAhg−1 to 261mAhg−1 when the post-treatment temperatures increase from 300°C to 500°C. The discharge capacities of the LiV3O8 cathode powders obtained after post-treatment at 400°C and 500°C are approximately 255mAhg−1 and 236mAhg−1, respectively, after 40 cycles.