Selenium is essential for humans and the deficit of Se requires supplementation. In addition to traditional forms such as Se salts, amino acids, or selenium-enriched yeast supplements, next-generation selenium supplements, with lower risk for excess supplementation, are emerging. These are based on selenium forms with lower toxicity, higher bioavailability, and controlled release, such as zerovalent selenium nanoparticles (SeNPs) and selenized polysaccharides (SPs). This article aims to focus on the existing analytical systems for the next-generation Se dietary supplement, providing, at the same time, an overview of the analytical methods available for the traditional forms. The next-generation dietary supplements are evaluated in comparison with the conventional/traditional ones, as well as the analysis and speciation methods that are suitable to reveal which Se forms and species are present in a dietary supplement. Knowledge gaps and further research potential in this field are highlighted. The review indicates that the methods of analysis of next-generation selenium supplements should include a step related to chemical species separation. Such a step would allow a proper characterization of the selenium forms/species, including molecular mass/dimension, and substantiates the marketing claims related to the main advantages of these new selenium ingredients.