Selenium (Se) is a naturally occurring metalloid element, which is essential to human and other animal health in trace amounts but is harmful in excess. Of all the elements, selenium has one of the narrowest ranges between dietary deficiency (40 gday1) and toxic levels (400gday1) (WHO, 1996), which makes it necessary to carefully control intakes by humans and other animals, hence, the importance of understanding the relationships between environmental exposure and health. Geology exerts a fundamental control on the concentrations of selenium in the soils on which we grow the crops and animals that form the human food chain. The selenium status of populations, animals, and crops varies markedly around the world as a result of different geological conditions. Because diet is the most important source of selenium in humans, understanding the biogeochemical controls on the distribution and mobility of environmental selenium is key to the assessment of selenium-related health risks. High selenium concentrations are associated with some phosphatic rocks, organic-rich black shales, coals, and sulfide mineralization, whereas most other rock types contain very low concentrations and selenium-deficient environments are far more widespread than seleniferous ones. However, health outcomes are not only dependent on the total selenium content of rocks and soils but also on the amount of selenium taken up into plants and animals—the bioavailable selenium. This chapter demonstrates that even soils containing adequate total amounts of selenium can still produce selenium-deficient crops if the selenium is not in a form ready for plant uptake