Ce³⁺ and Eu²⁺ doped alkaline earth aluminates MAl₂O₄ (M = Ca, Sr, Ba) were prepared by single-step combustion synthesis at low temperature (600 ℃). X-ray diffraction (XRD) analysis confirmed the formation of BaAl₂O₄, CaAl₂O₄, and SrAl₂O₄. Photoluminescence spectra and optimal luminescent properties of Ce³⁺ and Eu²⁺ doped MAl₂O₄ phosphors were studied. Relation between Eu²⁺ and Ce³⁺ f-d transitions was explained. Spectroscopic properties known for Ce³⁺ were used to predict those of Eu²⁺ by using Dorenbos’ method. The values thus calculated were in excellent agreement with the experimental results. The preferential substitution of Ce³⁺ and Eu²⁺ at different Ba²⁺, Sr²⁺, Ca²⁺ crystallographic sites was discussed. The dependence of emission wavelengths of Ce³⁺ and Eu²⁺ on local symmetry of different crystallographic sites was also studied by using Van Uitert’s empirical relation. Experimental results matched excellently with the predictions of Dorenbos’ and Van Uitert’s models.