Current research motivation on fabricating next‐generation lithium‐ion batteries by averting the growing demand for battery raw materials brings enormous interest on the V2O5 cathode again as a result of its abundance, ease synthesis, and tunable Li‐intercalation properties. So far, the research activities are mainly focused on V2O5 to attain a maximum capacity (>300 mAh g−1) for more than 1 mol. Li‐intercalation which results in poor structural stability. Keeping this issue in mind, here, the full‐cell assembly by limiting 1 mol is proposed and constructed. Li‐insertion in V2O5 as a cathode and LiC6 as an anode for the first time. Prior to the full‐cell assembly, hydrothermally prepared rod‐like V2O5 reveals the specific capacity of 143 mAh g−1 in half‐cell configuration with good cycling stability. The full‐cell, V2O5/LiC6, offers a specific capacity of ≈236 mAh g−1 with a maximum energy density of ≈197.1 Wh kg−1. Furthermore, the practical feasibility of the cell has been examined at different temperatures that divulged a maximum energy density of 136 Wh kg−1 at 50 °C. Also, the obtained results encourage V2O5 as a strong contender for the commercial LiFePO4/C system andpave the new directions for advanced battery technology.