Although Xuanyuan mirrors are hung within the curled dragon caisson ceiling in many structures in the Forbidden City, little research has been carried out concerning Xuanyuan mirror.In this paper, the Xuanyuan mirror and its accessories such as gourd-shaped painted enamelware in Wanchun Pavilion were analyzed using a variety of instrumental analysis methods. The analytical results indicate that the glass ball matrix of the Xuanyuan mirror is made of potassium-lead glass and that a tin amalgam technique was employed in the plating layer. The date of manufacture was later than the end of the 17th century. The analytical results of the decorative gourd-shaped painted enamel reveal that the chemical composition of the white base glaze is similar to “Glass white” material. The matrices of enamel glazes with different colors are also made of potassium-lead glass. Lead tin yellow plays a dual function as colorant and opacifier in the yellow enamel glaze. Lead arsenate is the opacifier in the blue enamel glaze, and gold particles are the colorant in the rouge red enamel glaze. The colorant material of the brown contour line is hematite. Most of the painted enamel glaze materials were pre-melted, and the white base glaze, brown contour lines and other colored enamel glazes were painted in sequence before final firing.