Capsules composed of poly(styrene sulfonate, sodium salt) (PSS)/poly(diallyldimethyl ammonium) chloride (PDADMAC) were prepared by layer-by-layer deposition of the polyelectrolytes on melamine formaldehyde colloidal templates followed by the decomposition of the cores by hydrochloride. A yield of more than 90% of intact capsules was achieved if (i) the core diameter was equal to or less than 3.8 mum and (ii) not more than five pairs of layers were adsorbed. When the cores were larger or the layers were thieber, the osmotic pressure difference caused by core dissolution led to an increased frequency of wall rupture. The elasticity modulus of a multilayer consisting of five pairs of PSS/PDADMAC was about 140 MPa as measured by osmotic pressure induced capsule deformation.