Black and white porcelain plays a critical role in Chinese decorative porcelain history. It is famous for its decorative styles and techniques, which create a strong black and white color contrast in its appearance. In this study, representative black and white porcelains produced in Shanxi province were analyzed by X‐ray fluorescence, Raman spectroscopy, and SEM‐EDS. The results show that both Ca‐rich (~5.33 wt%) and Ca‐poor (~1.99 wt%) glazes were used leading to quite different microstructures. The pigment particles of Ca‐rich glazes are characterized by small size (≤2 μm), wide distribution, and tightly wrapped by anorthite. In contrast, they are larger (≥2 μm) and tightly cumulated together in Ca‐poor glazes. Hematite is the major crystal in pigment, double‐substituted by Al and Ti. The Al/Fe ratios are similar, but Ti/Fe ratios are quite different: They do not exceed 0.03% in Ca‐poor glazes, whereas they reach 0.12% in Ca‐rich glazes, suggesting that the origin of the pigments must be different. Al‐rich mineral such as kaolin was added to the pigment preparation in Ca‐rich glazes. The color of the pattern is mainly influenced by the size, quantity, and concentration of brown Ti‐doping hematite, as well as the thickness of the glaze layer and other crystals and Fe ions. The fired atmosphere of Ca‐rich glaze type seems less oxidizing than for Ca‐poor glaze type. Overall, the results confirm that black and white porcelain has a variety of production techniques, which is attributed to the craftsman adjusting the techniques according to the composition of raw materials.