Electron microprobe analysis (EMPA) provides information on the chemical composition of minerals and their relationships in archaeological ceramics by utilizing a narrow electron beam to stimulate the emission of X-rays. Among various signals produced, the most important are the back-scattered electrons (BSE), the secondary electrons (SE) and the characteristic X-rays. The possibility to combine BSE images, SE images, elemental mapping and quantitative analysis offers a sound basis for integrated interpretation of the ancient ceramics. The precise compositional and fabric features resulted by EMPA are indicators of the raw materials and their provenance. Even when in small amounts, the composition of the newly formed phases enables narrowing down the technological constraints, such as firing temperature and atmosphere.