The roles of plaque and saliva in the initiation and progression of dental caries are summarised schematically in figure 1. A central feature is the generation of organic acids, such as lactic acid, by acidogenic plaque bacteria following the dietary intake of carbohydrates such as sucrose. As discussed in Chapter 1, saliva performs two direct functions in order to combat enamel dissolution by these acids: (a) the continuous flow of saliva acts to clear the acids from the mouth and (b) the supply of a number of diverse salivary constituents that have 'anticaries activity'. The latter constituents can act on the acids themselves, via buffering or neutralisation, on the bacteria, via inhibition of the metabolic processes involved in acid production, and on the enamel, by maintaining chemical supersaturation in the adjacent plaque fluid. A key indirect function of saliva is as a medium for the transfer of potentially active therapeutic agents, such as fluoride (F), to the site of action.The physical presence of plaque mediates all the above salivary functions through its influence on ionic and molecular transport, whilst plaque components also provide binding sites for many salivary constituents and therapeutic agents. This plaque 'reservoir' function is the theme of this chapter.First, we describe the chemical composition of plaque fluid in relation to caries, then the role of plaque structure. Next, we discuss the influence of F retained in plaque, including site-to-site differences, followed by the effect of treatments that seek to deposit plaque calcium (Ca) and/or inorganic phosphate (Pi). A combination of small sample volumes and low constituent concentrations typically leads to high measurement variability that results, in turn, with authors often having difficulty in discriminating between subject groups.