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Diagnostic investigations were carried out on a rare Chinese polychrome glazed ceramic dating back to the reign of the Xuande Emperor (1426–1435). The double-walled warming bowl was investigated using several non-invasive methods such as portable optical microscopy, endoscopy, portable X-ray fluorescence spectrometry, X-radiography, and computed tomography. One microsample was collected and analyzed by scanning electron microscopy with an energy dispersive X-ray detector. According to the results, the chemical composition of the paste suggested a porcelain typology, while the glaze belongs to the lead–barium–silicate (PbO-BaO-ZnO-SiO₂) system. These unexpected data contrast with common knowledge, which attests that the addition of barium in glass and ceramics manufacturing disappeared soon after the Han dynasty (206 BCE-220 CE). Moreover, the combination of PbO-BaO-ZnO-SiO₂ seems to be quite rare both in ancient pre-Han times and during the Ming and Qing dynasties. This paper aims to demonstrate that (a) the use of barium for glaze and glass composition, which seems to have its roots in Taoist alchemy, was not totally halted in later periods compared to the Han dynasty; (b) lead–barium–zinc–silicate glaze was used during the Xuande Emperor’s reign. Through a review of ancient Chinese literary sources, we found a lot of unpublished information on the use of barium, lead, and zinc in the production of glazed ceramics during this period. The polychrome glazed warming bowl suggests a particular production that flourished during the brief reign of the Xuande Emperor. Full article