This work demonstrated that the ligand symmetry of europium(iii) complexes controls the ratiometric luminescence characteristics of lanthanides. Nona-coordinated europium(iii) complexes having unsymmetrical β-diketonate ligands (Cs) exhibit distinctive ratiometric spectral variations in the extremely narrow f-f transition bands over the temperature range from 253 to 323 K. In contrast, no such ratiometric change can be observed in a series of nona-coordinated europium(iii) complexes containing symmetrical β-diketonate ligands (C2v). The remarkable difference depending on the ligand symmetry (Csvs. C2v) suggests that the coordination rearrangement of β-diketonate in the complex causes ratiometric spectral variations in extremely narrow f-f transition bands, where two europium(iii) complex isomers exist in the solution equilibrium. A self-calibration method using dual iso-emissive points is reported, where self-calibration using the two emission intensities at the iso-emissive points reduces the coefficient of variation in luminescence thermometry.