Pottery sherds from the archaeological site of Bancun (Henan, China) were analyzed by Raman microscopy and the pigments used in the coating of this ancient (c.4000–5000 BC) pottery were determined. It was found that bauxite was used to make the white pigment. The black coating was identified as a magnetite and its particle size was in the nanometer range. This work also showed that the size of pigment had influence on the color of the coating. In principle, Raman spectra could be used not only to identify the mineral source of the pigment but also to estimate the particle size of the pigments.