The formation of europium doped MeBr₂ microcrystals Me =Sr , Ba ) embedded in NaBr matrix is revealed in NaBr—MeBr₂—Eu crystalline system. The spectral-luminescent properties of embedded MeBr2—Eu microcrystals are studied upon the synchrotron radiation excitation. The mechanisms of luminescence excitation of europium centers in NaBr—MeBr₂—Eu crystalline system and features of Me²⁺ and Eu²⁺ impurity ions aggregation processes in NaBr matrix are discussed.