Alkaline earth aluminates with the overall nominal compositions Mg0.5Sr0.5Al2O4 (MSA), Ca0.5Sr0.5Al2O4 (CSA) and Ca0.5Mg0.5Al2O4 (CMA) doped with 0.5 or 1 mol% of Eu2+ ions were obtained by a modified aqueous sol-gel method and annealed in a reductive atmosphere at 900, 1000, 1100 and 1300 °C. The sample compositions and their structures were studied by XRD employing the Rietveld method. Solid solubility was confirmed in CSA only, due to the similar ionic radii of Ca2+ and Sr2+. UV excited luminescence was observed in the blue region (λ = 440 nm) in samples of CSA and CMA containing the monoclinic phase of CaAl2O4 and in the green region (λ = 512 nm) in samples of MSA containing hexagonal or monoclinic phases of SrAl2O4.