Microorganisms can remove metals from the surrounding environment with various mechanisms, either as metabolically mediated processes or as a passive adsorption of metals on the charged macromolecules of the cell envelope. Owing to the presence of a large number of negative charges on the external cell layers, exopolysaccharides (EPS)-producing cyanobacteria have been considered very promising as chelating agents for the removal of positively charged heavy metal ions from water solutions, and an increasing number of studies on their use in metal biosorption have been published in recent years. In this review, the attention was mainly focused on the studies aimed at defining the molecular mechanisms of the metal binding to the polysaccharidic exocellular layers. Moreover, the few attempts done in the use of EPS-producing cyanobacteria for metal biosorption at pilot scale and with real wastewaters are here reviewed, discussing the main positive issues and the drawbacks so far emerging from these experiments.