A method is developed to calculate the ligand field (LF) parameters and the multiplet spectra of local magnetic centers with open d and f shells in solids in a parameter-free way. This method proceeds from density functional theory and employs Wannier projections of nonmagnetic band structures onto local d or f orbitals. Energies of multiplets and optical, as well as x-ray spectra are determined by exact numerical diagonalization of a local Hamiltonian describing Coulomb, LF, and spin-orbit interactions. The method is tested for several 3d and 5 f compounds for which the LF parameters and multiplet spectra are experimentally well known. In this way, we obtain good agreement with the experiments for La 2 NiO 4 , CaCuO 2 , Li 2 CuO 2 , ZnO:Co, and UO 2 .