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A phosphor for Plasma Display Panel, BaMgAl10O17:Eu2+, showing a blue emission band at about 450nm was prepared by a solid-state reaction using BaCO3, Al2O3, MgO, Eu2O3 as starting materials with flux AlF3. The study of the behaviour of Eu in BAM phosphor was carried out by the photoluminescence spectra and the Rietveld method with X-ray and neutron powder diffraction data to refine the structural parameters such as lattice constants, the valence state of Eu, the preferential site of Mg atom and the site fraction of each atom. The phenomenon of the concentration quenching was around 2.25~2.3wt% of Eu due to a decrease in the critical distance for energy transfer of inter-atomic Eu. Through the combined Rietveld refinement, R-factor, Rwp, was 8.11%, and the occupancy of Eu and Mg was 0.0882 and 0.526 at critical concentration. The critical distance of Eu2+ in BAM was 18.8Å at 2.25% Eu of the concentration quenching. Furthermore, c/a ratio was decreased to 3.0wt% and no more change was observed over that concentration. The maximum entropy electron density was found that the modeling of β-alumina structure in BaMgAl10O17:Eu2+ correct coincided showing Ba, Eu, O atoms of z=1/4 mirror plane.