Agronomic biofortification of staple crops is an effective way to enhance their contents in essential nutrients up the food chain, with a view to correcting for their deficiencies in animal or human status. Selenium (Se) is one such case, for its uneven distribution in the continental crust and, therefore, in agricultural lands easily translates into substantial variation in nutritional intakes. Cereals are far from being the main sources of Se on a content basis, but they are likely the major contributors to intake on a dietary basis. To assess their potential to assimilate and biotransform Se, bread and durum wheat were enriched with Se through foliar and soil addition at an equivalent field rate of 100 g of Se per hectare (ha), using sodium selenate and sodium selenite as Se-supplementation matrices, in actual field conditions throughout. Biotransformation of inorganic Se was evaluated by using HPLC−ICP-MS after enzymatic hydrolysis for Se-species extraction in the resulting mature wheat grains. Selenomethionine and Se VI were identified and quantified: the former was the predominant species, representing 70-100 % of the total Se in samples; the maximum amount of inorganic Se was below 5 %. These results were similar for both supplementation methods and for both wheat varieties. Judging from the present results, one can conclude that agronomic biofortification of wheat may improve the nutritional quality of wheat grains with significant amounts of selenomethionine, which is an attractive option for increasing the Se status in human diets through Se-enriched, wheat-based foodstuff.