Layered nanosheets of a LiV₃O₈ cathode material were successfully prepared via a modified solid-state synthesis. The morphological changes of the layered nanosheets of the LiV₃O₈ cathode, which resulted from preparation at different temperatures, strongly affected the electrochemical performance of this cathode material. The layered nanosheets of the LiV₃O₈ cathode prepared at 500 °C delivered the highest electrochemical performance with initial charge and discharge capacities of 212 and 175 mAh g−1, respectively, when cycled between 1.5 and 4.0 V versus Li/Li+. The particulate morphology of LiV₃O₈ showed widths in a range of 100-145 nm and lengths between 1.0 and 2.5 µm. The layered nanosheet structure contributed to the increased electrochemical performance of LiV₃O₈ as a cathode material for applications in high-energy lithium-ion batteries.