By alternating adsorption of positively and negatively charged polyelectrolytes on the surface of the substrate (e.g. colloidal particles), thin films called polyelectrolyte multilayers are formed. In the case of adsorption on spherical nanoparticles it is possible (by removing the substrate) to prepare hollow spheres of micrometer and nanometer dimensions with various physico-chemical properties. Due to the large number of available polymeric compounds, these systems find their application in the fields of biomedicine, catalysis and functionalized nanomaterial synthesis. In this study, hollow nanospheres of weak polyelectrolytes, poly(allylamine) and poly(acrylic acid) were successfully synthesized, using hydroxyapatite particles as substrates. The formation of the polyelectrolyte multilayer on colloidal particles was monitored by measuring the electrophoretic mobility of the particles, and the removal of the substrate was obtained by dissolution in the presence of hydrochloric acid. The effective hydrodynamic diameter of the obtained polyelectrolyte capsules was determined by the method of dynamic light scattering, while information on the morphology and size of nanospheres was obtained by atomic force microscopy and scanning electron microscopy. Infrared spectroscopy and energy dispersion X-ray analysis confirmed the removal of the substrate.