Accurately quantifying selenium (Se) speciation and transformation in Se-enriched crops is highly significant for human health. The investigation of Se species in Se-enriched crops involves assessing the enrichment of both organic and inorganic Se species, considering their plant families and edible parts. The staple crops of rice, corn, and wheat showed no or less inorganic Se with the increase of total Se; however, potatoes expressed a proportion of selenate [Se(VI)]. In addition, the organic Se proportions in Se-enriched crops of Cruciferous, Brassicaceae, and Umbelliferae plant families were relatively lower than the proportion of inorganic Se. Concurrently, the edible parts of the Se-enriched gramineous or cereal crops enriched with organic Se and crops with fruit, stem, leaf, and root as edible parts contain the maximum percentage of organic Se with a certain proportion of inorganic Se. This study contributes to a sparse body of literature by meticulously discerning appropriate Se-enriched crop selection through a comprehensive evaluation of Se speciation and its organic and inorganic accumulation potential.