Polyelectrolyte multilayers composed of poly(allylamine hydrochloride) and poly(styrene sulfonate) were assembled on 13 nm gold nanoparticles and characterized by Transmission Electron Microscopy and Atomic Force Microscopy. The direct measurement of the interactions at the molecular level using a Surface Force Apparatus revealed that the colloidal stability of such coated particles in aqueous media is brought about concomitantly by electrostatic and steric repulsive interactions. The cyanide induced dissolution of the gold cores yields either hollow nanocapsules or collapsed nanospheres, two species which are very difficult to distinguish. In contrast to the established micron sized hollow capsules, the dissolution of the nanosized gold cores may induce a substantial swelling of the polyelectrolyte complex into the central void as induced by the temporary local increase of the ionic strength. At least three layer pairs are required to maintain the structural integrity of the polyelectrolyte shells to yield hollow nanospheres. At about three layer pairs, thin nanocapsules are mechanically compressible and may collapse on themselves following mechanical stimulation to form even smaller spherical polyelectrolyte complex particles that retain the small polydispersity of the gold cores. Thus, the templating of polyelectrolyte shells around, e.g., gold nanoparticles followed by the dissolution of the respective cores constitutes a new method for the synthesis of extremely small polyelectrolyte complex particles with very low polydispersity.