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The persimmon-red glazed wares, characterized by a reddish-brown appearance with high gloss, were one of the main varieties of glazes manufactured in Jian kilns (Fujian province, China) during the Song Dynasty. Densely packed dendritic ε-Fe 2 O 3 crystals in microns size composed of several branches were observed in the glazes surfaces of Jian persimmon-red wares. The branches, consisting of well-arranged rod-like crystals with offset around 110 or 220 nm, could serve as sub-micron mirrors to improve the glaze gloss. A number of Al and few Ti and Mn ions were detected to substitute Fe ions in ε-Fe 2 O 3 crystals. The Al substitution could play a dual role in ε-Fe 2 O 3 structure: (1) stabilizes the structure through increasing of cationic disorder and (2) makes the appearance less dark, which could account for the nice persimmon-red appearance of Jian wares. Besides, zircon, quartz, hematite, jacobsite and mullite were also observed in the glaze surfaces. • Dendritic ε-Fe 2 O 3 crystals in microns size composed of several branches were observed in the glazes surfaces of Jian persimmon-red wares. • The branches consisting of well-arranged rod-like crystals with offset ~110 or 220 nm could serve as sub-micron mirrors to improve glaze gloss. • Al substitutions in ε-Fe 2 O 3 crystals could play a dual role of acting as stabilizers to increase cationic disorder and making appearance less dark. • A few impurity crystals including zircon, quartz, hematite, jacobsite and mullite were detected in the glazes surfaces. [ABSTRACT FROM AUTHOR]