Computational and experimental methods are employed to study the optical properties of Dy-doped BaAl 2 O 4 matrix. Atomistic modelling is used to make predictions of Dy doping sites and charge compensation schemes. The symmetry predicts from atomistic modeling was used to calculate crystal field parameters and to obtain the energies of the electronic transitions of the Dy 3+ ion. Dy-doped BaAl 2 O 4 was prepared via a sol-gel proteic technique. The optical properties were studied using X-ray excited optical luminescence (XEOL) measurements. The X-ray absorption near-edge structure (XANES) at the Ba and Eu L III -edges exhibits typical absorption spectra. The area under the XEOL spectra increases as the photon energy increases in the region around the Ba and Dy L III -edges. The XEOL spectra showed typical Dy lines. Experimental and calculated values for the transition energies are compared.