The structural evolution of Li3V2(PO4)3/C upon cycling in different potential ranges was studied via XRD. The results reveal that the repeated charge/discharge processes would cause the loss of crystallinity and irreversible expansion of unit cell volume, both of which are related to the applied upper limit of potential. The highest degree of the crystallinity loss and irreversible expansion of unit cell volume of the Li3V2(PO4)3/C sample cycled in the range of 3.0-4.8V is considered to be partially responsible for the worst cycling performance among the three operating potential regions. On the contrary, no marked expansion of unit cell volume is observed when the upper limit of potential is extended from 4.3V to 4.6V. Accordingly, the Li3V2(PO4)3/C sample cycled in 3.0-4.6V delivers extra 17-37 mAh g−1 specific capacity over that of 3.0-4.3V with reasonable cycling stability. Therefore, the potential range of 3.0-4.6V would be the best operating potential region for the practical applications of Li3V2(PO4)3.