Incubation of CaCO3 microparticles in chitosan (CS) solution at pH 5.2 and following with ethylenediaminetetraacetic acid disodium salt (EDTA) treatment resulted in CS single-component microcapsules with an ultra-thick wall structure. Repeating the incubation caused stepwise increase of wall thickness and finally resulted in CS microcapsules with a layered structure. This unique method is mediated by precipitation of CS on the CaCO3 particles as a result of pH increase caused by the partial dissolution of CaCO3. The obtained CS capsules are stable at neutral pH.