The Yaozhou kiln complex is a representative production center of ancient northern China, famous for the celadon production. In this work, bubbles, glassy matrix and residual crystals of celadon glazes produced from the Tang to Yuan Dynasty were analyzed by using optical microscopy, Raman spectroscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS). The results revealed that the Song, Jin and Yuan productions present bigger bubble and higher area ratios of the Si-O bending over stretching modes than the Tang and Wudai productions. This is consistent with firings at higher temperatures during Song, Jin and Yuan Dynasties. It is also in agreement with the historical studies, which revealed the change from wood-firing to coal-firing during Song Dynasty. The observation of calcium phosphate in Yaozhou productions indicated that the glaze ash had been used. No iron-based particle was identified by Raman spectroscopy in the glazes of all periods. The green color is certainly due to iron ion dispersed in the glassy matrix. Our study also confirmed no significant change in glaze raw materials used for Yaozhou productions from Tang to Yuan Dynasty.