AbstractSelenium (Se) is a naturally occurring essential micronutrient that is required for human health. Selenium supports cellular antioxidant defense and possesses bioeffects such as anti‐inflammation, anti‐cancer, anti‐diabetic, and cardiovascular and liver protective effects arising from Se‐enhanced cellular antioxidant activity. Past studies on Se have focused on elucidating Se speciation in foods, biofortification strategies to produce Se‐enriched foods to address Se deficiency in the population, and the biochemical activities of Se in health. The bioavailability and toxicity of Se are closely correlated to its chemical forms and may exhibit varying effects on body physiology. Selenium exists in inorganic and organic forms, in which inorganic Se such as sodium selenite and sodium selenate is more widely available. However, it is a challenge for safe and effective supplementation considering inorganic Se low bioavailability and high cytotoxicity. Organic Se, by contrast, exhibits higher bioavailability and lower toxicity and has a more diverse composition and structure. Organic Se exists as selenoamino acids and selenoproteins, but recent research has provided evidence that it also exists as selenosugars, selenopolysaccharides, and possibly as selenoflavonoids. Different food categories contain various Se compounds, and their Se profiles vary significantly. Therefore, it is necessary to delineate Se speciation in foods to understand their impact on health. This comprehensive review documents our knowledge of the recent uncovering of the existence of selenosugars and selenopolysaccharides and the putative evidence for selenoflavonoids. The bioavailability and bioactivities of these food‐derived organic Se compounds are highlighted, in addition to their composition, structural features, and structure–activity relationships.