The stable and reliable red phosphor with high-photon energy emission (620-650 nm) is critical for the fabrication of the phosphor-converted white light-emitting diode (WLED) with low correlated color temperature and high color rendering index. Mn ⁴⁺-activated phosphor is an emerging kind of red-emitting phosphor for WLED. Herein, the energy levels transition and photoluminescence characteristics of the Mn ⁴⁺ ion were introduced; then, the preparation, crystal structure and luminescent properties of as-far reported seven kinds of Mn ⁴⁺-doped oxyfluoride red phosphors (such as Na₂WO₂F₄:Mn ⁴⁺) containing d ⁰, d ¹⁰ or s ⁰ cations were reviewed. Currently, only in quite rare case of oxyfluoride, Mn ⁴⁺ was found to exhibit strong R-line emission, with local coordination remaining as either [MnF₆] or [MnO₆]. The studies on the chemical stability and quantum efficiency of Mn ⁴⁺-doped oxyfluoride phosphors are still insufficient. Finally, we prospected the future development of Mn ⁴⁺-doped oxyfluoride phosphor.