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The importance of selenium (Se) for medicine, industry and the environment is increasingly apparent. Se is essential for many species, including humans, but toxic at elevated concentrations. Plant Se accumulation and volatilization may be applied in crop biofortification and phytoremediation. Topics covered here include beneficial and toxic effects of Se on plants, mechanisms of Se accumulation and tolerance in plants and algae, Se hyperaccumulation, and ecological and evolutionary aspects of these processes. Plant species differ in the concentration and forms of Se accumulated, Se partitioning at the whole‐plant and tissue levels, and the capacity to distinguish Se from sulfur. Mechanisms of Se hyperaccumulation and its adaptive significance appear to involve constitutive up‐regulation of sulfate/selenate uptake and assimilation, associated with elevated concentrations of defense‐related hormones …