The consumption of dietary supplements has a significant increase in recent years mainly for a great appeal of this product in relation to a complementation of the diet with essential elements and an improvement and maintenance of health. The combination of increased consumption and free access to this product, associated to the lack in the inspection by government, makes their consumption uncontrolled and a potential risk to the citizen health. In this scenario the development of analytical methods for quality control, including a determination of the total selenium concentration and its species becomes a primordial necessity. For this, methodologies were developed for quantification of total selenium by ICP-MS and its inorganic species (Se IV and Se VI) and selenomethionine by HPLC-ICP-MS in samples of selenium-based food supplements and in isotopically enriched yeast sample in 78Se. The methodology for total selenium determination was optimized by experimental design and the limits of detection were in the range of 0.01 mg kg(-1) (CH4) and 0.1 mg kg(-1) (NH3) and the agreement with the CRM Selm-1 were between 99 percent (NH3) and 104 percent (CH4). The results found for selenium content in the food supplements samples presented a discrepancy in relation to the labeled value between -29 percent and + 170 percent and, complementarily, coupling of HPLC to ICP-MS allowed an speciation analysis in the food supplements samples. The use of the ICP-MS, HPLC-ICP-MS and ESI-MS techniques enabled a characterization of a 78Se isotopically enriched yeast sample in terms of its isotopic distribution, total selenium concentration and selenomethionine as well as proteins with molecular weight of approximately 12 kDa.