Fluorescence flame spectrometry is based upon the absorption of radiation by an atomic vapor to produce excited atoms, and the measurement of the radiation emitted when a fraction of these excited atoms lose their energy by a radiational process or processes called atomic fluorescence. Mitchell and Zemansky [1] and Pringsheim [2] have discussed much of the original research on the fluorescence of atomic vapors in quartz containers. However, the first reference to the fluorescence of atomic vapors in flames was reported in 1924 by Nichols and Howes [3] who observed the atomic fluorescence of calcium, strontium, barium, lithium, and sodium in a Bunsen burner flame. In 1927, Badger [4] published a classic paper on the atomic fluorescence of thallium, mercury, magnesium, copper, silver, cadmium, and sodium in an ordinary Bunsen burner flame as well as in a separated flame. Few references to flame fluorescence can be found between the years 1927 and 1962. However, in 1962, Alkemade [5] discussed the principles of atomic fluorescence flame spectrometry, particularly with regard to the measurement of quantum efficiencies. In 1964, Winefordner and Vickers [6] published the first paper on atomic fluorescence flame spectrometry as an analytical method. Since then, numerous manuscripts concerning the basis [7–9], the instrumentation [10–20], and the possible uses and advantages [21–35] of atomic fluorescence flame spectrometry have been published. In this chapter, the basis, instrumentation, and current and possible future uses of flame fluorescence spectrometry will be discussed.