This review deals with liquid phase separation of major arsenic and selenium species followed by element specific detection. The species-selective trace elements analysis is critically evaluated with particular emphasis on the use of techniques combining high performance liquid chromatography(HPLC) with an element specific detectors(e.g. AAS, ICP or ICP-MS). The potential and limitation of hyphenated techniques as a tool for speciation of arsenic and selenium compounds in environmental materials is discussed using a number of examples drawn from the latest research papers.