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The microprobe EDXRF equipment was used for analysis of the major and trace elements in glaze layer-transitive layer-body layer of the celadon from the Altar Yao (Kiln) and Laohudong Yao in the Southern Song Dynasty (1127-1279 A.D.), Zhejiang, China. The K values of the discriminant factor for the celadon wares are larger than 8, which means the celadon of the Altar Yao and Laohudong Yao are different from that of the Longquan Yao. The former two belong to the Guan Yao system (the Chinese imperial kilns), but the latter to the Min Yao system (the Chinese popular kilns). The principle component analysis shows their relationship between the Altar and Laohudong wares with provenance postulation. The thickness of the transitive layer in the Altar and Laohudong wares is obviously different, which reveals the microstructure characteristics of the celadon even though both kinds of wares belong to the imperial kiln system.