Rechargeable Li-based electrochemical cells are regarded as the most promising candidate for electric vehicle (EV) applications. High-capacity cathode combined with Li anode is a excellent and realizable choice to promote the endurance of rechargeable Li batteries. In this paper, single phase of zirconium pyrovanadate ZrV2O7 was first synthesized via sol-gel method in a low sintering temperature of 500°C. The Li-absent mixed-metal-oxide ZrV2O7, previously regarded as negative thermal expansion (NTE) material only, revealed a high specific capacity of 282.6mAhg−1 and a voltage plateau of 2.48V vs. Li as potential cathode for rechargeable Li batteries. These findings suggest that the ZrV2O7 after further optimization can be employed as high-capacity electrode for rechargeable Li batteries.