The great concern about the availability of lithium is leading to an increasing interest in sodium ion batteries. Sodium is very abundant and widely available throughout the world, which make sodium-ion technology an attractive candidate for the development of large battery systems. Currently, the lack of well-performing cathode has been a limiting factor in the successful implementation of Na-ion technology. Therefore, there is a need to develop cathode materials in sodium ion batteries that can sustain long cycle life and display reasonable gravimetric capacity that can potentially challenge the lithium ion battery technology. In this regard one of the polyanion-based cathodes, Na3V2O2(PO4)2F, is emerging as a viable candidate due to its high gravimetric capacity and long cycle-life. Recently it has been shown that Na3V2O2(PO4)2F can be cycled between NaV2O2(PO4)2F and Na4V2O2(PO4)2F leading to the possibility of achieving a theoretical energy density of 600 Wh Kg–1. However, there is a challenge in the synthesis of phase pure composition of Na3V2O2(PO4)2F. The unwanted by-product and the tendency of solid solution formation between the full fluoro and the oxo-fluoro derivatives, Na3V2O2x (PO4)2F3-2x (0 ≤ x ≤ 1), have created some confusion about the optimum performance of this material. In this presentation we will report a one-step soft chemical approach for the synthesis of phase pure Na3V2O2(PO4)2F and their single-crystal X-ray structure determination. There is some new insights in terms of location of Na ion as emerged from single-crystal solution of this compound in tetragonal system and I4/mmm space group. The detail electrochemical activities of this material towards Na- and Li-ion batteries along with other spectroscopic and magnetic characterization will be presented.