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The release of elements from dental casting alloys is a continuing concern because of the potentially harmful biological effects the elements may have on local tissues. The surfaces of the alloys appear to be most important in controlling the release of these elements. In the current study, the surfaces of high-, reduced-, and no-gold dental alloys were analysed by X-ray photoelectron spectroscopy before and after they were exposed to a biological medium for up to 96 h. The goal was to relate the release of elements from these alloys to their surface composition, and to determine the depth of the effect of the medium. The depth of the effect of the exposure was determined by argon milling of the alloy surface after exposure to the medium. Elements that were released into the medium were measured by means of atomic absorption spectroscopy. The release of elements from alloys was greater when the atomic ratio of noble to non-noble elements at the surface was less than 1. The depth of the effect of the medium varied with the alloy, but was always less than 100 A. The surface composition was significantly different from layers only 5 A below. It was concluded that the surface concentration of noble elements is important in controlling the release of non-noble elements from these alloys, and the surface composition appeared to be only one or two atomic layers thick. Of the three types of alloys, the high-gold alloy appeared to develop the most stable surface composition which released the lowest levels of elements.