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In field experiments, tartary buckwheat and hybrid buckwheat were foliarly sprayed with an aqueous solution of sodium selenate (20 mg Se L–1). In treated plants, the selenium content was significantly higher than in controls, irrespective of the plant part and taxon of buckwheat. The highest average Se concentrations in hybrid and tartary buckwheat were found in seeds. The main Se species found in seeds was Se methionine. Selenium-sprayed plants had higher photochemical efficiency of photosystem II in both taxa and higher electron transport system activity in hybrid buckwheat, suggesting a positive effect of Se on physiological characteristics. Because of the concentration of Se in both buckwheat taxa and selenomethionine as the dominant species of Se, Se-enriched buckwheat is a potential source of dietary Se for animals and humans.