Hexagonal neo-formed crystallites have been observed in thin section of different medieval and post-medieval lead-glazed ceramics. Although they are clearly visible in thin section using plane polarized light, their plate shape makes them barely seen on the polished cross sections. Basal sections have never been found on the polished sections and only few transversal very thin sections could be seen. In this case, the morphology resembles acicular and it is not possible to analyze them properly by SEM–EDX because the crystals are very thin and the glaze surrounding is analyzed as well. Micro-Raman microscopy was carried out directly on the polished thin sections. This technique allows specific areas as small as 1 µm in diameter to be analyzed and it is able to characterize inclusions that are not found on the glaze surface. However, the wavenumber features observed cannot be assigned to a specific compound. The thickness of the crystallites (a few hundred nanometers) seems to be responsible for the low sensitivity of the Raman instrumentation. 15¿×¿15 µm2 micro-X-ray diffraction patterns using synchrotron radiation (SR-µXRD) in transmission geometry were obtained from the crystals using the same thin section preparation. SR-µXRD was able to localize the crystallites and avoid the overlapping signals corresponding to other mineral phases. In this way, the hexagonal crystallites present in the glaze have been unambiguously identified as hematite crystallites. Finally, some replications were made under laboratory-controlled conditions to determine the firing conditions in the formation of those crystallites. The presence of hematite coexisting with melanotekite indicates a firing temperature <925°C, while the presence of only hematite suggests a firing temperature >925°C