The properties of rat liver acid-volatile selenium have been compared with those of H(2)Se and (CH(3))(2)Se. 2. In model experiments oxidation-sensitive H(2) (75)Se was trapped quantitatively under anaerobic conditions in 0.1m-AgNO(3), and (CH(3))(2) (75)Se was trapped quantitatively in 8m-HNO(3). The acid-labile selenium of a liver homogenate, and of a microsomal fraction, was found to behave quite unlike (CH(3))(2) (75)Se and in a manner indistinguishable from H(2) (75)Se. 3. It was concluded that the acid-volatile material is certainly not (CH(3))(2)Se and that it is probably H(2)Se. 4. The significance of these findings is discussed in relation to current knowledge about the metabolism and detoxication of selenium, and a scheme is proposed which incorporates this knowledge with recent observations on the interactions between trace amounts of selenium and tocopherol, and the production of acute selenium deficiency by Ag(+) in vitamin E-deficient rats.