This study deals with the incorporation of Eu3+ ions in aluminates with magnetoplumbite (MP) or mixed β alumina - MP type structure. The synthesis procedure is the coprecipitation from a nitric solution. Partial substitution of Eu3+ byLa3+ increases the thermal stability range of the phases. In these structuresEu3+ occupies several sites and in the case of Na+ containing phases, Eu3+ and Na+ coexist at some mirror planes. Some results concerning Cs+ ion immobilization in mixed β - MP structures, by ionic exchange in molten salt are also reported.