Scanning electron microscopy (SEM), in combination with quantitative elemental analysis, provides a powerful technique for studying the microstructure of ancient ceramics. The primary aim of such studies is to elucidate the production technology in terms of the raw materials used, the methods of decoration and the firing procedures. A similar approach can be used to extract information on metal production processes from the associated refractory ceramic debris (e.g., furnace linings, tuyeres, etc.). To illustrate the power of the SEM, information thus obtained on production technology is presented for Greek Attic red-figure ware, Chinese blue-and-white porcelain and Iznik ware, as well as for glass and other vitreous materials such as faience and Egyptian blue. The role of transmission electron microscopy, which can reveal finer details of ceramic microstructures, is also briefly discussed, and the need to consider ceramic technology in its wider cultural context is emphasised.