The suitability of hyphenated USAED with HPLC separation and ET-AAS determination as a new rapid methodology for Se control in Se-enriched food supplements is demonstrated. Total Se determination and Se speciation are accomplished in a single sample treatment using low sample amounts (ca. 10 mg), and low extracting volume (1 mL). The total Se content in seven of the 10 Se-enriched supplements studied was in agreement with the values obtained after microwave pressurized acid digestion, MW, (test t, p = 0.05). The Se species studied were Se(IV), Se(VI), SeMet, SeMeSeCys, and SeCys2, being some of the most common found in the 10 supplements studied. Although SeMet was the Se species expected to be present at the highest concentration in most Se-enriched food supplements, we detected it in only three of the 10 samples studied. In the other seven samples, two of them had Se(IV) as the main Se species. The other five supplements had Se species that did not match with any of the five standards selected by us. We have also systematically demonstrated that ultrasonication does not alter the following Se species: Se(IV), Se(VI), SeMet, SeMeSeCys, and SeCys2. The new procedure can be easily adapted to more Se species and can be routinely used for Se control in Se-enriched food supplements. Concerning the supplements studied, our results suggest that stricter control on the Se content in enriched food supplements in terms of Se species will need to become mandatory.