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Since the 18th century many analytical methods have been used to identify the chemical composition of archaeological artefacts, the provenance of the raw materials and the technical aspects of the manufacturing process. These techniques generally probe the bulk chemical and structural features of the objects and overlook surface characteristics often essential for understanding the manufacturing techniques and the ageing processes. This work describes the contribution of x-ray photoelectron spectroscopy (XPS) combined with bulk analytical techniques such as scanning electron microscopy + energy − dispersive spectrometry (SEM + EDS), inductively coupled plasma mass spectrometry (ICPMS) and x-ray diffraction (XRD) by discussing the origin of the embrittlement of some selected series of silver Republican Roman coins and the study of the microchemical nature of black and coral red glosses on Attic figured vases. The results show that XPS, if allowance is made for contamination or unrepresentative or non-homogeneous samples, complements the existing bulk analytical techniques and can provide detailed information about the surface chemical nature of the archaeological objects, as well as about their present state, and lead to recommendations for restoration and preservation.