The chemical composition and petrographic features of 51 samples of fine pottery selected from the archaeological site of Syracuse have been established by means of optical microscopy and X-ray fluorescence spectrometry, with the aim of creating a reference group for the ceramics produced in this important Greek colony during the Hellenistic–Roman period. This reference group is constrained by the analysis of six kiln wasters and of raw materials outcropping in the studied area. Among the studied findings, the main part is assignable imputably to local production, while some specimens probably come from Greece and other colonies (Messina and Gela). The Syracuse fine pottery is characterized by inclusions formed mainly by quartz and micaceous and fossiliferous groundmass. The used pastes were more or less purified through the removal of the sandy-to-coarse silty granulometric fraction. The multivariate statistical analysis of chemical data permits the identification of production at Syracuse on the basis of comparison with the kiln wasters and the Plio-Pleistocene clays.