Crystalline phases present in pigments scratched off the surfaces of some decorated ceramic sherds belonging to the Cucuteni Neolithic culture were successfully identified using synchrotron radiation X-ray diffraction at Daresbury Laboratory. The ceramic sherds were selected from a collection of the National Museum of Romanian History in Bucharest. The synchrotron radiation X-ray diffraction analysis revealed that the black-color pigments on the surface of a number of sherds were produced by a variety of jacobsite (Fe2MnO4) phases; magnetite (Fe3O4) was also found in one of the sherds. The red color was derived from clay slips with a high content of hematite (Fe2O3). Calcite (CaCO3) was found in the white pigments; its presence was explained as being related to postburial deposition processes. Conclusions on technological aspects, provenance, and conservation issues are given.