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Sherds of ancient ceramics potteries, dating back to the seventh century BC and excavated from southern Italy, were analyzed in terms of microstructure and porosity (SEM), elemental composition (EDX), chemical bonding and mineralogical components (FTIR) in order to establish correlation with firing temperature, firing condition and provenance. Si/Al ratio from EDX analysis showed three major categories of raw materials (illite/montmorillonite, kaolinite and mullite), suggesting difference in provenance. Uniformly sized silica nanoparticle (0.7 μm diameter) and trace amount of silver are being reported for the first time in one sample. Anorthite mineral and quartz inclusion was detected by FTIR in certain samples. All samples showed a prominent band for Si-O stretching, which shifted from 1062 cm−1, broadened and appeared as doublet, relative to processing temperature. FTIR results proved incomplete dihydroxylation and undissociated carbonate in three samples, indicating a firing temperature of 700–800°C, whereas other samples were fired above 900°C. Only one sample among these three showed bloating pores in between interconnecting glassy matrix in SEM image, indicating a firing temperature of 1100–1200°C. The absence of magnetite along with significant Fe and Mn content indicated the formation of jacobsite, an iron manganese spinel complex, MnFe2O4, which is responsible for the black gloss effect in two particular samples and can be further confirmed by XRD. The presence of numerous small pores in SEM image of one of these two samples (1.2 μm diameter) was indicative of extended vitrification at higher temperature than the other one. However, magnetite was responsible for black gloss effect in two other samples, proving difference in provenance. Therefore, SEM-EDX and FTIR results can offer valuable insight into the firing conditions, gloss decoration and provenance of ancient ceramic potteries. [ABSTRACT FROM AUTHOR]