Red phosphors BaTiF₆:Mn⁴⁺ with microrod and polyhedron morphologies have been prepared respectively by etching TiO₂ and Ti(OC₄H₉)₄ in a HF solution with an optimized concentration of KMnO₄ at 1.5 mmol L⁻¹ in hydrothermal conditions. The red phosphor BaTiF₆:Mn⁴⁺ exhibits a broad excitation band in the blue region and sharp emission peaks in the red region. A white LED (WLED) fabricated with the red phosphor BaTiF₆:Mn⁴⁺ shows “warm” white light that possesses a color rendering index of 93.13 at a color temperature of 4073.1 K.