An ab initio calculation of the optical absorption spectrum of Mn2+‐doped CaF2 is performed in which electrostatic and quantum embedding effects originated by a relaxed and polarized CaF2 lattice on the ligand field ground and excited states of a MnF86− cluster have been considered. The theoretical spectrum is calculated by means of the complete active space self‐consistent‐field (CASSCF) and average coupled pair funtional (ACPF) methods, correlating up to 23 electrons. An excellent overall agreement with the experiments is found and a detailed analysis of the results is presented. The initial assignment of the 4A1g(4G) and 4Eg(4G) states, lately reversed, is supported. The wrong assignment of the 4T1g(4P) state is shown to be responsible for a recently proposed change of the value of the crystal field splitting paramenter initially accepted, 10Dq=4250 cm−1, which is in turn supported here. Also, new assignments for the absorptions to the 4T1g(4F) and 4T2g(4F) excited states are suggested.