Counterions present at the surface of polyelectrolyte multilayers were utilized for the introduction of charged species into the multilayer via ion exchange. A typical polyelectrolyte multilayer film with Na(+) counterions in the outermost layer was immersed in an AgNO(3) aqueous solution and the rapid ion-exchange process was complete within 1 min. The silver ions thus introduced were then reduced in situ and silver nanoparticles were produced at the surface of the multilayer assembly. This example demonstrates that the counterions naturally occurring in every polyelectrolyte multilayer film can be a convenient vehicle for the introduction of various functionalities to the film. (C) 2009 Elsevier B.V. All rights reserved.