Absorption, emission, and excitation spectra covering a wide energy range of 3000-58000 cm -1 for the Eu 3+ ion in the low symmetry system K 5 Li 2 EuF 10 have been reported. The emission spectra have been analyzed by taking into account the influence of the temperature onto the luminescence from the 5 D 0,1,2 multiplets. The observed energy intervals in transition bands characteristic for the europium ion have been assigned and modeled using a multistep approach developed for this system. A risk of producing numerical artifacts in the multidimensional parameter space has been minimized by its strong reduction based on the enhanced angular overlap model and standardization of the low symmetry crystal field. The reported results are satisfactory (the final rms error of the fitting below 9.2 cm -1 ), consistent in each step of the procedure and in line with the microscopic physicochemical picture of the crystal field effective interaction.