The emergence of white porcelain represents a crucial breakthrough in the history of Chinese ceramics, laying a technological foundation for the subsequent prosperity of blue-and-white and painted porcelains. It is widely regarded as the “fourth milestone” in the history of Chinese ceramic science and technology. Therefore, the origination of white porcelain is a pressing issue in the fields of archaeology and archaeometry, which focuses on the remains of the Northern Dynasties and Sui Dynasty from the Xing kiln site excavated in 2012. In this study, inductively coupled plasma-mass spectrometry (ICP-MS) and thermoelectric ionization mass spectrometry (TIMS) were used to analyze the raw materials for early Xing wares from the Fuwulou kiln site in Neiqiu, providing scientific evidence as to the evolution of early porcelain technology at Xing kiln. The results show that the early Xing ware bodies can be divided into two categories based on the trace element pattern, indicating that two kinds of raw materials were used for making porcelain. It further shows that the Xing potters intentionally selected a higher-quality raw material distinct from that of celadon for the production of new wares. The early white porcelain contains generally lower levels of trace elements such as V, Cr, Ni, Nb, Ta, Zr, and Hf, which are closely related to the impurities of zircon and rutile. The strontium (Sr) isotopic mixing pattern analysis demonstrates that the glaze-making for early Xing ware did not generally follow the recipe of wood ash mixed with body clay, but rather that it was mixed with other glaze-making clays. Furthermore, there are discrepancies in strontium isotopic compositions between the early white porcelain and celadon glaze, suggesting that Xing potters attempted to improve the whiteness by modifying the glaze-making technology. These findings scientifically reveal the raw material characteristics and sources of early Xing wares and provide valuable insights into the origination of white porcelain.