S Neutron activation analysis has been employed for the characterization of Samian ware sherds. The analysed samples were classified in ten groups, seven of which belonged to the Arretine production, according to archaeological evidence. By means of high resolution gamma‐ray spectroscopy, 22 elements have been identified and analysed. Compositional characterization was looked for by taking counting rate ratios of different nuclides in the samples. The compositional pattern of the sherds was found to be fairly uniform both for each pot and for each group so that, at least in the examined cases, it can be assumed to be characteristic of a given workshop.