Li0.6Na2.4V2(PO4)(2)F-3 holding a NASICON structure is synthesized via ion exchange from Na3V2(PO4)(2)F-3. The Na+ ions at Na(2) sites and inserted Li+ ions in this NASICON structure are suggested to give a large initial specific capacity and a hybrid-ion migration during electrochemical cycling. As a lithium-inserted cathode material, Li0.6Na2.4V2(PO4)(2)F-3 exhibits a specific capacity of 123 mAhg(-1) at a current density of 0.1C with two plateaus around 3.77 and 4.19 V vs. Li+/Li. The capacity of the Li0.6Na2.4V2(PO4)(2)F-3/Li battery can retain 104 mAhg(-1) with a high coulombic efficiency of 98.6% at 0.1C after 151 cycles. (C) 2015 Elsevier B.V. All rights reserved.