Red K 2 LiGaF 6 :Mn 4+ phosphors have been synthesized by the facile cation-exchange method. To optimize the optical properties, the phosphors were synthesized by using different reaction conditions. The highest luminescence intensity was increased 3.6 times for the Mn concentration of 1%, reaction temperature of 20 C, and reaction time of 1 h. Replacement of the trivalent Al by Ga resulted in K 2 LiGaF 6 :Mn 4+ having better photoluminescence properties than K 2 LiAlF 6 :Mn 4+ . Furthermore, the studies of the temperaturedependent emission intensity of the phosphors confirmed their good thermal stability, making them promising red phosphor candidates for white light-emitting diodes.