Selenium consumed by humans in foods and in supplements exists in a number of different organic and inorganic forms including selenomethionine, selenocysteine, selenate and selenite. Animal and human studies have established that the bioavailability of the selenium depends upon the chemical form, which also influences the distribution of selenium in the body. These studies have included urinary excretion of selenium following ingestion of different forms of selenium, and the response of tissue selenium concentrations and activities of functional selenoproteins to these selenium compounds. Selenomethionine is retained in tissue proteins to a greater extent than selenocysteine and the inorganic forms, but the selenium is not necessarily immediately available for functional selenoproteins. A number of other factors besides chemical form may also influence the bioavailability and distribution of selenium, including other dietary components, selenium status, physiological status and species. Knowledge of these factors and of speciation of selenium in foods, tissues and functional selenoproteins is important for the accurate assessment of selenium status. Speciation of selenium also has implications with respect to the determination of selenium requirements and to the investigation of relationships between selenium status and health and disease.