A mass of Longquan celadon shards were excavated from the Chuzhou site of Huai'an City in Jiangsu Province, China. These celadon shards were fired during the period of the Late Yuan Dynasty to the Tianshun era of the Ming Dynasty, as identified by archaeologists at Nanjing Museum. In order to research the chemical composition features of this ancient celadon porcelain, energy dispersive X-ray fluorescence (EDXRF) for non-destructive analysis was used to determine the chemical composition of the porcelain body and glaze in these shards. The results indicate that Ti and Fe in the body of Longquan celadon are characteristic elements which can distinguish porcelain produced during the Late Yuan Dynasty from those produced in the Ming Dynasties. The results of the principal component analysis (PCA) show that different body and glaze raw materials were used for the production of porcelain in different periods and the raw materials of the body and glaze are also different for various vessel shapes. The chemical compositions in the porcelain body of civilian ware are slightly different. The imperial and civilian Longquan celadon porcelains produced during the Hongwu era to the Tianshun era of the Ming Dynasty are distinguishable by the MnO, Fe2O3, Rb2O and SrO content in their porcelain glaze.