Dadiwan culture in the Weihe River Basin gave birth to the earliest painted pottery in China. The production of painted pottery reflected not only the level of people’s understanding and utilization of nature at that time, but also the spiritual world of the Dadiwan ancestors. In order to better understand the Dadiwan ancestors’ knowledge of the white pigments of painted pottery, we analyzed the chemical composition, phase composition and thermal properties of four white (light) lump pigments from the Dadiwan site, using scanning electron microscopy (SEM-EDS), X-ray diffraction (XRD), Raman spectrometry (Raman), real-time infrared spectrometry (RTIR) and thermogravimetric analysis-differential scanning calorimetry (TG-DSC) . The results show that white massive pigments can be divided into two main categories. One is carbonate. QD1 (Dadiwan Phase II) and QD2 (Dadiwan Phase IV) contain mainly quartz, dolomite, muscovite and chlorite, etc. The other category is aluminosilicate clay minerals. The white part of QD3 (Dadiwan Phase IV) contains mainly quartz, amorphous peraluminosilicate (probably metakaolinite and potassium feldspar), cristobalite, mullite and ilmenite, etc.; the red part is hematite particles; calcium carbonate was deposited on the surface of the sample. QD4 contains mainly quartz, muscovite, albite and kaolinite; calcium carbonate was deposited on the surface of the sample. This research provides data for the further understanding of raw material processing and the level of pottery-making by Dadiwan ancestors.