Owing　to　the　magnetic　dipole　nature,　the　zero　phonon　line　(ZPL)　of　Mn4+:2E　→　4A2　transition　is　weak　unless　Mn4+　is　situated　at　a　site　deviating　from　the　centrosymmetric　nature.　Herein,　we　report　a　brand-new　oxyfluoride,　Na2WO2F4:Mn4+(NWOF:Mn4+),　which　shows　unprecedented　intense　red　ZPL　at　∼620　nm　along　with　relatively　weak　vibronic　transitions　under　blue　light　excitation.　This　peculiar　spectral　feature　is　demonstrated　to　be　originated　from　the　highly　distorted　octahedral　coordination　environment　in　the　C2v　group　symmetry　surrounding　Mn4+.　High-resolution　spectroscopic　studies　at　10　K　disclose　the　fine　structured　electronic/vibronic　transitions　of　Mn4+:2E,　2T1　→　4A2　and　the　weak　electron-phonon　interaction　(Huang-Rhys　factor　S　4+　emissive　state.　Benefiting　from　the　intense　ZPL,　an　ultra-high　color　rendering　index　with　Ra　=　92.7　and　R9　=　90.0　is　achieved　in　the　w-LED　using　YAG:Ce3+and　NWOF:Mn4+　as　color　converters,　and　a　wide　color　gamut　of　107.1%　NTSC　in　the　w-LED　using　CsPbBr3　quantum　dots　and　NWOF:Mn4+　is　obtained.　Herein,　we　first　demonstrate　that　Mn4+-activated　oxyfluorides　have　great　potential　in　w-LED　lighting　and　display　applications.　Our　study　can　also　enlighten　researchers　to　design　highly　distorted　octahedral　sites　for　Mn4+　doping　to　achieve　an　ultra-intense　ZPL.　©　2017　The　Royal　Society　of　Chemistry.