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Lithium-ion capacitors, as a hybrid electrochemical energy storage device, realize high specific energy and power density within one device, thus attracting extensive attention. Here, hierarchically porous Li 3 VO 4 /C nanocomposite is prepared by a solvo-thermal reaction, followed with a post-annealing process. This composite has macropores at the center and mesopores in the wall, thus effectively promoting electrolyte penetration and structure stability upon cycling simultaneously. Compared to mesoporous Li 3 VO 4 , the enhanced rate capability and specific capacity of hierarchically porous Li 3 VO 4 /C indicate the synergistic effect of mesopores and macropores. Inspired by these results, this composite is coupled with mesoporous carbon (CMK-3) for lithium-ion capacitors, generating a specific energy density of 105 Wh kg −1 at a power density of 188 W kg −1 . Even if the power density increases to 9.3 kW kg −1 , the energy density still remains 62 Wh kg −1 . All these results demonstrate the promising potential of hierarchically porous Li 3 VO 4 in lithium ion capacitors. [ABSTRACT FROM AUTHOR]