This paper presents the results from the pilot analytical study of the Aegean Late–Final Neolithic/Anatolian Middle–Late Chalcolithic (c. 5500–3200/3000 BC) pottery from the Kastro-Tigani settlement, located in south-east Samos (east Aegean). In addition to Crete, the region of the insular eastern Aegean has produced the earliest evidence for Neolithic habitation. The archaeological traces at Kastro-Tigani are so far the earliest known on Samos, being partly contemporary with the recently discovered Middle–Late Chalcolithic layers at the Heraion, lying in close proximity to the former site, and at the Agriomernos cave (Megalo Seitani) in the north-west part of the island. The re-evaluation of the ceramic assemblage from Kastro-Tigani has led to the laboratory analysis of 34 samples, using a combination of thin-section petrography and Wavelength Dispersive X-Ray Fluorescence Spectroscopy, in order to determine provenance and establish reference groups for the earliest local production on Samos. This first compositional characterisation of the pottery contributes new data in a relatively under-studied region and provides grounds for comparison with analytical results from the Heraion, with the aim to investigate possible relations between the sites. Hence, the identification of different strategies in pottery production, reflected in the overall distinct fabric and chemical groups, further indicates the practice of several production units and the exploitation of various raw material sources at the Pythagoreion/Chora plain. Isolated examples of possible imported ceramic vessels, as well as exotica (e.g. obsidian, acrolithic and Kilia figurines, ring-shaped features, marble vessels, kratiriskoi) are highlighted as markers of macro-scale interaction in the context of Aegean early maritime connectivity.