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The phase diagram of the CsBr-CaBr2 system was re-determined by using differential thermal analysis and high temperature and room temperature X-ray diffraction analysis. It is concluded that there are three intermediate compounds in this system: a congruently melting compound, CsCaBr3, with a melting point of 823℃ and two incongruently melting compounds, Cs2CaBr4 and Cs3Ca2Br7, whose peritectic points being 597℃ and 635℃, respectively. X-ray diffraction analysis indicated that compound CsCaBr3 is of slightly distorted perovskite structure.