Nondestructive Raman spectroscopy and external-beam proton-induced X-ray emission (PIXE) technique to analyze eight ancient glasses unearthed from the provinces of Henan, Hubei, and Jiangsu, which allowes for a good characterization of the glass matrix and chemical compositions, is carried out. The results indicate that all the eight glass samples could be typically divided into three systems: faience (sample No. SZWG-4), PbO-BaO-SiO2 (sample Nos. NYWKI-5-1, HNWKII-88, and HNWKII-84), and Na2OCaO-SiO2 (sample Nos. HBWKI-16, HBWKI-17, HBWKI-18, and SZWG-1). Additional relationships between the Raman spectra and parameters, such as residues of raw materials and opacifying agent, are also discussed by respectively comparing them with similar glass samples excavated from other historical sites.