The modern analytical SEM, which can provide high-quality imaging facilities together with quantitative elemental analysis using an energy-dispersive spectrometer, is finding wide application in the investigation of archaeological problems. Many of these investigations involve the study of silicate and carbonate-based artefacts which may be relatively unmodified from their original geological parent raw materials so that mineralogically based interpretations are often appropriate. In this paper we present a series of examples illustrating the role of the analytical SEM in the mineralogical investigation of archaeological problems, including the characterization and provenancing of geological raw materials, the elucidation of the processes used to transform those raw materials into useful objects and the recognition and characterization of changes which archaeological artefacts may have undergone during burial or during storage.