During the construction of the stations on lines 1 and 6 of the Naples underground, located in Piazza Santa Maria degli Angeli, in Piazza Nicola Amore and in Piazza Municipio, a significant number of Western Greek amphorae were discovered. A selection of thirty-seven fragments were selected, dated to the 6th and 4th centuries B.C., and classified according to the typological characteristics proposed by Sourisseau and Gassner for the rim shape variants and then subjected to archaeometric analysis. This type of amphora was produced in several centers across Magna Graecia (Sicily), in the Ionian-Adriatic region, the Aegean and Massalia, indicating its wide distribution throughout the central-southern Mediterranean. The presence of multiple workshops in different sites makes it challenging to pinpoint specific production centers. The selected fragments were analyzed using a multi-analytical approach with different techniques, such as thin section analysis with a polarized-light microscope (PLM) and chemical analysis via X-ray fluorescence (XRF). Mineralogical analysis by X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) were also performed to determine the technological features of the samples. By comparing the petrographic evidence with the chemical data, their possible origin areas were recognised. The thin section analysis allowed us to identify seven petrographic groups with homogeneous characteristics and four outliers. Chemical data, combined with Hierarchical Cluster Analysis (HCA), confirmed the results of the petrographic observations, grouping samples characterized by high concentrations of chromium and nickel and samples with lower concentrations of calcium oxide. The results of the analyses made it possible to identify a local production of Western Greek amphorae, as well as productions linked to the Paestum area, the Calabria region and the Aegean/Ionian-Adriatic region.