A new type of monoethanolamine (MEA) and Mn⁴⁺ co-doped KTF : MEAH⁺, Mn⁴⁺ (K₂TiF₆ : 0.1MEAH⁺, 0.06Mn⁴⁺) red emitting phosphor was synthesized by an ion exchange method. The prepared Mn⁴⁺ co-doped organic–inorganic hybrid red phosphor exhibits sharp red emission at 632 nm and the emission intensity at room temperature is 1.43 times that of a non-hybrid control sample KTF : Mn⁴⁺ (K₂TiF₆ : 0.06Mn⁴⁺). It exhibits good luminescent thermal stability at high temperatures, and the maximum integrated PL intensity at 150 °C is 2.34 times that of the initial value at 30 °C. By coating a mixture of KTF : MEAH⁺, Mn⁴⁺, a yellow phosphor (YAG : Ce³⁺) and epoxy resin on a blue InGaN chip, a prototype WLED (white light-emitting diode) with CCT = 3740 K and R_a = 90.7 is assembled. The good performance of the WLED shows that KTF : MEAH⁺, Mn⁴⁺ can provide a new choice for the synthesis of new Mn⁴⁺ doped fluoride phosphors.