Rod-like LiV3O8 composites have been fabricated by using a carbamide-assisted rheological phase reaction method. The electrochemical performances of the LiV3O8 materials prepared under different conditions are investigated by cyclic voltammograms, galvanostatic charge–discharge tests and electrochemical impedance spectroscopy (EIS). The rod-like LiV3O8 calcined at 500°C has the optimal performance, delivering an initial discharge capacity of 273.6 and 250.4mAhg−1 between 2.0V and 4.0V at a current density of 50 and 120mAg−1, respectively. After 60 cycles by applying 50mAg−1, a discharge capacity of 213.0mAhg−1 is obtained, showing a good cycling performance. The EIS studies show that the 500°C-LiV3O8 electrode has very low impedance increase during 1st to 240th discharge-charge cycles. All these results indicate that the rod-like LiV3O8 compound has a promising application as the cathode material for rechargeable lithium batteries.