This paper presents a comparative description of different methods of determination of arsenic, antimony and selenium: spectrophotometric, electro-analytical (voltamperometry), activation analysis, atomic fluorescence and the methods of inductive or microwave-induced plasma in combination with different detection methods (emission or mass spectrometry). The description is based on literature data illustrating the present state of the metalloid determinations in different matrices. The limits of determination ensured by different methods are also compared. Much attention has been paid to methods combining chromatographic separation with selective detection, especially with the application of plasma generation methods (usually ICP-MS).