A bilayer of a hydrophobically modified polyelectrolyte, octadecyl poly(acrylamide) (PAAm), sandwiched between the layers of a hydrophilic polyelectrolyte, poly(ethyleneimine) (PEI), is prepared by the sequential electrostatic-hydrophobic-electrostatic- interaction-driven self-assembly on planar and colloid substrates. This process results in a PEI/[PAAM](2)/PEI-multilayercoated substrate. The removal of a PAA/PEI/[PAAM](2)/PEI-multilayer-coated decomposable colloidal template produces hollow capsules. Irregular hydrophobic domains of the [PAAm](2) bilayer in the PEI/[PAAM](2)/PEI-multilayer capsule are infiltrated with a lipid to obtain a uniform, distinct hydrophobic layer, imparting the capsule with a pseudobilayer vesicle structure.