Selenium (Se) deficiency and toxicity affect over a billion people worldwide. Plants can mitigate both problems, via Se biofortification and phytoremediation. Here we explore the potential of hemp (Cannabis sativa L.) for these phytotechnologies. Field surveys in naturally seleniferous agricultural areas in Colorado, United States, found 15−25 μg of Se/g in seed and 5−10 μg of Se/g dry weight (DW) in flowers and leaves. Thus, 4 g of this hemp seed provides the U.S. recommended daily allowance of 55−75 μg of Se. In controlled greenhouse experiments, hemp seedlings grown in Turface supplied with 40−320 μM selenate showed complete tolerance up to 160 μM and accumulated up to 1300 mg of Se/kg shoot dry weight. Mature hemp grown in Turface supplied with 5−80 μM selenate was completely tolerant up to 40 μM selenate and accumulated up to 200 mg of Se/kg DW in leaves, flowers, and seeds. Synchrotron X-ray fluorescence and X-ray absorption spectroscopies of selenate-supplied hemp showed Se to accumulate mainly in the leaf vasculature and in the seed embryos, with predominant Se speciation in C−Se−C forms (57−75% in leaf and more than 86% in seeds). Aqueous seed extracts were found by liquid chromatography mass spectrometry to contain selenomethionine and methyl-selenocysteine (1:1−3 ratio), both excellent dietary Se sources. Floral concentrations of medicinal cannabidiol (CBD) and terpenoids were not affected by Se. We conclude that hemp has good potential for Se phytoremediation while producing Se-biofortified dietary products.