The state-of-the-art of species-selective analysis for trace metals and metalloids in biological materials by chromatographic and electrophoretic separation techniques with element selective detection is critically reviewed. The species of interest include organoarsenic, organoselenium and metal complexes with bioligands such as phytochelatins, metallothioneins, proteins and polysaccharides. The separation mechanisms discussed include size-exclusion, anion- and cation-exchange and reversed-phase HPLC and flatbed and capillary zone electrophoresis. Advantages and limitations of various element selective (e.g., AAS, ICP-AES and ICP-MS) and molecule specific (electrospray MS/MS) detection techniques used on- and off-line are discussed. The applications of coupled techniques to the analysis of biological materials are comprehensively reviewed in tabular form. Attention is paid to the sample preparation and sources of error in bioinorganic speciation analysis.