Mn4+-activated BaTiF6 red phosphor has been synthesized by chemical reaction method from HF, H2SiF6, BaF2, KMnO4, and titanium sponge. The optical properties of BaTiF6:Mn4+ are investigated using photoluminescence (PL) analysis, PL excitation spectroscopy, luminescence decay time measurement, and Raman scattering spectroscopy. The sharp red emission peaks at ∼635 nm with luminescence decay time of ∼10 ms are observed at temperatures between T = 20 and 300 K. Further increase of T results in the PL intensity quenching of Eq ∼ 0.45 eV, which is in good agreement with that determined from the luminescence decay time vs T data. The unique temperature dependence of the PL intensity is also observed at T ∼ 20 − 300 K and is well explained by the proposed calculation model. Comprehensive discussion is given on the Mn4+-related luminescence properties of a family of dialkaline and alkaline-earth hexafluorometallate phosphors. The Raman scattering spectra for the pure and Mn4+-doped BaTiF6 crystals are also examined.