A red pigment was often used for decorating the surface of different style classes of pottery during the Middle Ages in the South of Italy. This work is concerned with the identification of the red pigment on ceramic ware, both lead-glazed and unglazed painting, coming from the medieval archaeological sites of Castel Fiorentino (Foggia), the Cathedral of Bari, Torre di Mare (Matera) and Gallana (Brindisi). X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM) with Energy Dispersive X-ray Spectroscopy (EDS) and Raman Microscopy were used as analytical techniques to investigate the decorated surfaces. The results suggest that the red colour is due to lead compounds in the glazed fragments and in the painted ones from Bari Cathedral, to iron oxides in the Castel Fiorentino painted shards and to a mixture of lead and iron compounds in the Gallana painted ware.