77Se and1H nuclear magnetic resonance spectra have been measured for selenols (RSeH), diselenides (RSeSeR), and selenenyl sulfides (RSeSR′), including selenenyl sulfides formed by reaction of glutathione and penicillamine with selenocystine and related diselenides. Exchange processes strongly affect the77Se and1H nuclear magnetic resonance spectra of all three classes of compounds. Sharp, exchange-averaged resonances are observed in the1H nuclear magnetic resonance spectra of selenols; however, selenol proton exchange causes the77Se resonances to be extremely broad over the pH range where the selenol group is titrated. Selenol/diselenide exchangealso results in exchange-averaged1H resonances for solutions containing RSeH and RSeSeR; however, the77Se resonances were too broad to detect. Exchange reactions have similar effects on nuclear magnetic resonance spectra of solutions containing selenols and selenenyl sulfides. The results indicate selenol/diselenide exchange is much faster than thiol/disulfide exchange. The77Se chemical shift depends on the chemical state of the selenium, e.g., titration of the selenol group of selenocysteamine causes the77Se resonance to be shielded by 164 ppm, oxidation of the selenol to form the diselenide selenocystamine causes a deshielding of 333 ppm, and oxidation to form the selenenyl sulfideresults in a deshielding of 404 ppm.77Se chemical shifts were found to be in the range −240 to −270 ppm (relative to (CH3)2Se) for selenolates, approximately −80 ppm for selenols, 230–360 ppm for diselenides, and 250–340 ppm for selenenyl sulfides. The77Se chemical shift is also affected by titration of neighboring carboxylic acid and ammonium groups, and their pkAvalues can be calculated from77Se chemical shift data.