At present, spectroscopy analysis has become an important technical means to support the development of archaeometry, and has played an important role in origin research, coloring mechanism, dating analysis, etc. The Xipo site in Lingbao city, Henan Province, with its rich Yangshao culture remains, has been identified as one of the first-choice sites for “the exploration of Chinese civilization”. Lingbao area is the central area of Miaodigou type of Yangshao culture, which may correspond to the archaeological culture sites in the Yellow Emperor era. Therefore, many archaeological experts believe that the exploration and excavation of Xipo site will help discover the mystery of the origin of China’s 5 000-year-old civilization. Xipo site is also rich in unearthed relics, including pottery, jade, stone tools, and some special green frits, which predate the appearance of proto-porcelain glazes by more than 1 000 years. This study uses ICP-MS/AES, EPMA, Raman spectroscopy analysis techniques to analyze 50 pieces of pottery and 1 piece of frit unearthed from Xipo site in Lingbao city, Henan Province. The pottery unearthed at Xipo Site is mainly red pottery and brown pottery. At the same time, there were painted pottery, red leather pottery (pottery with red coating), yellow pottery, black ash pottery, etc. Previous studies mainly attributed different colors of pottery to different firing atmospheres, and did not discuss the source of raw materials for different types of pottery. Based on the measurement of 16 trace elements in argillaceous pottery and multivariate statistical analysis, the source characteristics of different kinds of pottery are discussed. At the same time, the microstructure of some painted pottery and the phase compositions of black color were studied, and the structural characteristics of green frit unearthed from the site were analyzed. The results show that the Ba content in the raw materials of the clay used in most pottery with red coating is relatively high, which is different from other potteries and may have a special source of raw materials. Magnetite is the coloring mineral raw material for the black color on the painted pottery surface. The chemical composition of the green frit is close to that of the proto-porcelain except for the low manganese and phosphorus content. These results provide a scientific basis for understanding pottery making techniques and social production in Yangshao period. The study shows that the combination of various spectroscopic analysis techniques based on elemental analysis and structural analysis has achieved remarkable results in the research of archaeological materials.