The theoretical rationalization of the open-shell 4f and 5d configuration of Eu2+ is by far not trivial because it involves a non-standard version of ligand field theory, based on a two-shell Hamiltonian. Here we present our methodology based on ligand field theory, taking the system CsCaBr3:Eu2+ as a case study with an octahedral coordination sphere of Eu2+. The ligand field, interelectronic and spin-orbit coupling parameters are deduced from experimental data. The assignment of the transitions to the corresponding irreducible representations of the double group was performed together with the intensity modelling resulting in an excellent match to the experimental spectra. (c) 2015 Elsevier B.V. All rights reserved.