Multiple methods composed of three-dimensional ultra-depth of field video microscope, laser Raman spectroscopy, X-ray fluorescence spectroscopy, Scanning electron microscopy with energy dispersive spectrometer, and colorimeter were applied to analyse the composition and microstructures of two kinds of Liubo chess pieces with different textures and colors uncovered from the tomb of Warring States period in Shaanxi province. The blue samples were identified as lead-barium glass, and the purple samples were Chinese Purple products. Moreover,a new kind of product of Chinese Purple in the Warring States period was discovered. The composition of lead-barium and the glass products of the samperiod recovered from Shaanxi, Hunan, Hubei, and Sichuan was also compared. It is speculated that the fabrication of lead-barium glass in the Warring States period has matured, and different composition ratios can be carried out according to the needs of the shape of the objects. What's more, glass production also had the phenomenon of remelting old materials to make new ones. Based on determining the composition of Chinese Purple, the colorimeter was used to get spectral data, according to which the characteristic spectral peaks were determined for the artificial copper barium silicate pigment for the first time. It is possible to identify this kind of pigment rapidly and non-destructively.