Within the frame of an in-depth study of the corpus of about 560 western Greek transport amphorae (6th–5th century BC) yielded from excavations at the necropolis of the Dorian-Chalcidian colony of Himera in North-western Sicily, one of the most interesting issues consists in the determination of their provenance. Based on archaeological considerations, nearly 100 items have been attributed to southern Campania, specifically to Poseidonia and Elea. The present paper proposes a detailed combined archaeological-archaeometric investigation of 16 samples discovered at Himera and one at Jerba (Tunisia), of presumed Campanian provenance, compared with 4 local reference samples from Poseidonia and 6 samples of western Greek amphorae found at Pithekoussai and Elea, attributed to Poseidonia by previous archaeometric analysis. All samples have been submitted to a macroscopic fabric examination according to the standard methods of FACEM (Fabrics of the Central Mediterranean) and to petrographic investigation (polarised light microscopy) and digital image analyses of microstructures. Our study points to a Campanian provenance of the investigated amphorae and their distinction in a large group from Poseidonia and a small group from Elea. The identification of a numerous assemblage of 5th century BC Poseidonian transport vessels at Himera substantially underlines an earlier hypothesis about its ‘Campanian connection’ and allows for the reconstruction of an important Tyrrhenian commercial axis.