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UDC 546.161;535.37:(538.958+538.955) We have studied the effect of CaF 2 :Eu luminophore synthesis methods on the charge state of europium. We have shown that Eu 3+ predominates over Eu 2+ in samples obtained by coprecipitation of europium with calcium fluoride, and the ratio Eu 3+ /Eu 2+ grows as the total amount of europium increases. Partial charge conversion of the europium occurs during calcination of the samples, due to changes in the excess fluorine balance. We studied the luminescence, magnetic susceptibility, and EPR of the synthesized samples. We have shown that in a solid solution, europium forms large ordered clusters, determining both the luminescent and the magnetic properties of the material.