Novel microcapsules were prepared from colloidal coreshell particles by acid dissolution of the organic core. Weakly crosslinked, monodisperse and spherical melamine-formaldehyde polycondensate particles (diameter 1 mu m) were synthesized as core template and coated with multilayers of an anionic polyelectrolyte via layer-by-layer deposition technique. As polyelectrolytes, an anionic naphthalenesulfonate formaldehyde polycondensate that is a common concrete superplasticizer and thus industrially available, and cationic poly(allylamine hydrochloride) were used. Core removal was achieved by soaking the coreshell particles in aqueous hydrochloric acid at pH 1.6, resulting in hollow microcapsules consisting of the polyelectrolytes. Characterization of the template, the coreshell particles, and the microcapsules plus tracking of the layer-by-layer polyelectrolyte deposition was performed by means of zeta potential measurement and scanning electron microscopy. The microcapsules might be useful as microcontainers for cement additives. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013