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Phase chemical relation of quaternary systems KBr-REBr3-HBr (13%)-H2O (25℃, RE=La, Sm) were determined, and the rule of phase change was also discovered bere when RE are light rare earth elements. It is found from the experiment that the quaternary systems in which KBr and REBr3 react in hydrobromic acid belong to a simple eutectic type,so the reaction mechanism for synthesizing compound K2REBr5 type and real action of the first step reaction can be explained with Meyer’s method. Furthermore, it can be seen from comparison between the systems in this paper and the system CsBr-REBr-HBr (13%)-H2O (25℃) that CsBr and REBr3 acting in hydrobromic acid with each other can form doublecompound easier than KBr and REBr3.