Polyphosphates are important but neglected polyelectrolytes that play a major role in biology and in surface science for the stabilization of colloids against flocculation and for the preservation of food. They are also known as "Calgon" and intensively used as additives in washing powders. This review aims to review recent developments in which linear polyphosphates are used for the design of new functional coatings using sol-gel processes and layer-by-layer deposition methods. All these methods rely on the high charge density of polyphosphates as inorganic polyelectrolytes, therefore the structure and properties of these molecules are also reviewed. New perspectives will also been given for the design of stimuli responsive coatings at the tiny frontier between biology and materials science. (C) 2014 Elsevier B.V. All rights reserved.