Built by the royal family in the Ming Dynasty, the Da Bao En Temple is known as the greatest temple in ancient Nanjing, whose predecessor is the Chang Gan Temple built in the Six Dynasties. Archaeological excavations of the Da Bao En Temple and the underground palace of Chang Gan Temple built in the North Song Dynasty (AD960-AD1127) have been appraised as one of the 10 greatest archaeological discoveries in 2010 in China. Many artefacts discovered in the underground palace have shown their important historical meanings and scientific values, such as the Qibao King Asoka Tower, golden and silver coffins, Buddhist relics, the silk textiles, glasses, and spices etc. In this paper, stereomicroscope, SEM-EDS and LA-ICP-AES are used to investigate chemical composition, microstructure and current preservation status for the unearthed glasswares. The results indicate that the glass bottle coded as TH1 and the glass calyx coded as TN5 are made of lead-silicate glass, while the chemical composition of the glass bottle coded as TN9 is quite distinct from that of native glasswares. All three articles have been weathered in some degrees. Given the shape, it is deduced that TH1 is a typical glassware used in burying Buddhist relics at that time, TN5 a domestic glassware with typical Sassanian style, and TN9 an imported Islamic glass, providing important information about culture exchanges between China and the foreign countries in the North Song Dynasty.