The electronic structure of Eu²⁺ compounds results from a complex combination of strongly correlated electrons and relativistic effects as well as weak ligand-field interaction. There is tremendous interest in calculating the electronic structure as nowadays the Eu²⁺ ion is becoming more and more crucial, for instance, in lighting technologies. Recently, interest in semiempirical methods to qualitatively evaluate the electronic structure and to model the optical spectra has gained popularity, although the theoretical methods strongly rely upon empirical inputs, hindering their prediction capabilities. Besides, ab initio multireference models are computationally heavy and demand very elaborative theoretical background. Herein, application of the ligand-field density functional theory (LFDFT) method that is recently available in the Amsterdam Modeling Suite is shown: (i) to elucidate the electronic structure properties on the basis of the multiplet energy levels of Eu configurations 4f⁷ and 4f⁶5d¹ and (ii) to model the optical spectra quite accurately if compared to the conventional time-dependent density functional theory tool. We present a theoretical study of the molecular Eu(ƞ⁹-C₉H₉)₂ complex and its underlying photoluminescence properties with respect to the Eu 4f-5d electron transitions. We model the excitation and emission spectra with good agreement with the experiments, opening up the possibility of modeling lanthanides in complex environment like nanomaterials by means of LFDFT at much-reduced computational resources and cost.