Aqueous zinc-ion batteries (ZIBs) represent an attractive choice for stationary energy storage. Its widespread application relies on the development of novel, reliable cathode materials. Herein, we find NASICON structured Na3V2(PO4)3 manifests simultaneous Zn2+/Na+ intercalation/de-intercalation in a single component electrolyte (2.0 M Zn(CF3SO3)2). The Na3V2(PO4)3/rGO microspheres prepared by spray drying deliver a high specific capacity of 114 mAh g−1 with an average discharge platform of 1.23 V at 50 mA g−1. Impressively, a high capacity of 74 mAh g−1 can be obtained after 200 cycles at 500 mA g−1. These excellent electrochemical performances can be ascribed to the stable and open NASICON framework, fast ion diffusion, as well as continuous electron transport. This work sheds light on the development of secondary batteries with hybrid ion intercalation/de-intercalation behaviors using a single component electrolyte.