This paper presents the chemical characterization of 79 fragments of Archaic and Hellenistic fine-grained pottery from archaeological sites in Messina, Catania, Lentini and Siracusa (Sicily). The sherds were classified as ‘calcidian’, ‘banded’, ‘unvarnished’ and ‘black varnished’ pottery. The major and trace elements identified by X-ray fluorescence (XRF) were statistically elaborated using the method proposed by J. Aitchinson in 1986 for the analysis of compositional data. From cluster analyses using element/SiO2 log-ratios, it was possible to group the pottery found in Catania, Lentini and Siracusa into highly linked clusters. Conversely, the Messina pottery was divided into two clearly distinct groups. With the aim of identifying any possible mineralogical differences between the two Messina groups, Fourier transform infrared (FT–IR) absorption measurements were made, showing only quantitative differences in plagioclase and muscovite. The specific groups of pottery with restricted chemical compositions are considered to be of local production, also on the basis of archaeological and petrographic evidence.