Analyzing the ZPL could be beneficial in the explorationof structure–property relationships. A correlation betweenthe ZPL intensity and degree of deviation of the MnF6octahedral clusters from the ideal octahedral symmetry isobserved. These techniques are valid for all fluoride phosphors, in which the ZPL can be properly identified. Finally,the higher LER for the fluoride phosphors with stronger ZPLintensity has facilitated the study for future narrow-emissionred phosphors.