Studies of the setting of glass-ionomer cements have been carried out for over twenty years, and there is now a considerable body of information concerning the steps that lead to the conversion of a freshly mixed cement paste into a solid, durable dental restorative. This paper reviews these studies, paying particular attention to more recent work. The conclusion is that glass-ionomers consist of interpenetrating networks of inorganic and organic components forming a matrix in which particles of unreacted glass are embedded. However, there remain uncertainties over aspects of the setting chemistry, for example over the role of (+)-tartaric acid in the setting reaction, and over the nature of the fluoride species which form during the reaction. The chemistry of resin-modified glass-ionomers is also discussed and shown to be more complex than that of the simple cements. The presence of the resin component slows down the ionic cure reaction of the conventional cement, and leads to both a significant exotherm and a set material capable of absorbing water reversibly. The paper concludes that the microstructure of the set cement depends completely on chemical composition and the kinetics of the setting process, and that an understanding of the setting chemistry of these materials is thus important for optimal clinical use.