NASICON-type structured Na3V2O2(PO4)2F nanocubes with multi-wall carbon nanotubes (MWCNTs) composite has been synthesized by ethylene glycol-assisted hydrothermal reaction and used as a rechargeable non-aqueous and aqueous sodium-ion battery cathode material. As a cathode material for non-aqueous sodium-ion batteries, as-synthesized Na3V2O2(PO4)2F-MWCNT composite shows stable capacity of 98 mAh g−1 at 0.1 C for 120 cycles and 60 mAh g−1 at 2 C for 1800 cycles in half-cell and full-cell configurations, respectively. In aqueous electrolytes, Na3V2O2(PO4)2F-MWCNT composite delivers discharge capacity of 35 mAh g−1 at 1 C rate in half-cell and 42 mAh g−1 at 1 C rate in full-cell with NaTi2(PO4)3-MWCNT as an anode. Stable cyclability and high rate performance of Na3V2O2(PO4)2F-MWCNT nanocomposite can be attributed to the very short sodium ion diffusion length in nano cube morphology of Na3V2O2(PO4)2F as well as the carbon nanotubes matrix which endows the unbreakable conductive networks for electrons and Na+ ions.