The Eu 2 + doped alkaline earth aluminates, MAl 2 O 4 :Eu 2 + (M = Ca and Sr) co-doped with selected R 3 + ions are efficient new persistent luminescence materials. The detailed mechanisms of persistent luminescence are not yet known. The importance of the defects to induce persistent luminescence was studied here by EPR, Mossbauer, thermoluminescence (TL) and persistent luminescence measurements. The EPR results show that even the non-doped material, CaAl 2 O 4 , contains trapped electrons, probably in anion vacancies. Similar EPR properties are shown by the Eu 2 + doped and R 3 + co-doped materials. Other paramagnetic defects are present, too. The Mossbauer results indicated complex distribution of the Eu 2 + ions in the CaAl 2 O 4 host. Different R 3 + ions affect the thermoluminescence and persistent luminescence properties of the CaAl 2 O 4 :Eu 2 + , R 3 + materials in a very different manner, from enhancing to total suppression.