In order to study the composition, structure and status of preservation of polychrome potteries excavated from a Chu tomb of the Warring States period in Taoyuan County, Hunan Province, we used energy dispersive X-ray fluorescence (EDXRF) spectrometry, scanning electron microscopy-energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD) and laser Raman spectrometry (LRS), etc. to analyze the chemical compositions of pottery bodies and pigments on pottery surfaces and metal coatings. The chemical compositions of pottery bodies, which are made from fusible clay, are similar. The red pigment on pottery surfaces is cinnabar (HgS) and the black is carbon black (C). According to the SEM-EDS and XRD analyses, a layer of tin, as a typical decoration, was identified on pottery surfaces. By Fourier transform infrared (FTIR) spectrometry, the black material on the inner side of the tin layer is mainly lacquer, along with other types of binding materials. This paper provides new data for future research on the craftsmanship and development of tin-decorated pottery during the Warring States period.