Marine microorganisms are capable of successfully colonizing toxic surfaces through the formation of biofilm structures. In this article, most of the literature reporting the presence of marine biofilms on chemically-active antifouling paints is briefly reviewed. Of special concern is the influence of the dense extracellular polymeric substances (EPS) matrix on the release rate of the compounds involved in antifouling paint performance (i.e. active compounds and controlled-release binder molecules). A deeper understanding of these phenomena is of interest for both environmental legislators and paint formulators.