The toxicity, mobility, bioavailability and bioaccumulation of metals are dependent on the particular physico-chemical form in which the element occurs in the environment. Special attention has been paid to metals which are essential for the proper functioning of organisms if present in appropriate amounts but are toxic if in excess (i.e. Se, Cr), and also to non-essential elements (i.e. Hg, Pb, Cd, Sn and As). To assess the potential hazard to the health of marine organisms, qualitative and quantitative analyses of metal species accumulating along the food chain needs to be carried out. This paper reviews the available information on the speciation of trace elements in the food chain in marine ecosystems and the analytical tools used for acquiring reliable information in this field. Advantages and limitations of commonly used techniques indicate that all metal species in different samples need diverse extraction, separation and detection conditions. Although not recommending which procedure is the most suitable to determine a given compound, speciation analysis has the potential to be a powerful tool for the identification of trace element species in biological samples.