Polyanionic Na3V2(PO4)(2)FO2 has been successfully prepared for the first time by ionothermal reaction in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMIM TFSI) ionic liquid. Its structure and elemental stoichiometry are confirmed by X-ray diffraction, NMR spectroscopy, and ICP-OES, respectively. Furthermore, the scanning electron microscopy reveals that the as-obtained material possesses an original platelet-like morphology. A topochemical reaction mechanism is proposed to explain the formation of the 3D framework of Na3V2(PO4)(2)FO2 from layered compound aVOPO(4)-2H(2)O. Galvanostatic electrochemical tests indicate a modification of the desodiation and sodiation mechanism of the as-prepared Na3V2(PO4)(2)FO2 compared to those synthesized by conventional solid-state approaches. Furthermore, the electrochemical performance of Na3V2(PO4)(2)FO2 obtained at different cycling rates is also discussed.