Dipalmitoyldiphosphatidic acid (DPPA), dipalmitoyldiphosphatidylcholine (DPPC), and sphingosine were adsorbed onto polyelectrolyte coated colloids and capsules forming composite lipid-polyelectrolyte layers. The stepwise coating was performed either by adsorption of preformed vesicles onto the capsule surface or by a solvent exchange protocol. The lipid assembly was monitored by zeta-potential measurements. Single particle light scattering, flow cytometry, and fluorescence studies of Forster energy transfer have been used to quantify the lipid coating. Confocal microscopy images of capsules coated with fluorescent lipids demonstrated a homogeneous coverage of the capsule surface. Differential scanning calorimetry shows a phase transition temperature characteristic for lipid layer structures. It was concluded that the adsorbed DPPA form bilayers while DPPC may form multilayers. It was further shown that on top of the lipid layers further polyelectrolyte layers could be assembled. The permeability of B-carboxyfluorescein (6-CF) through the composite layer structure was studied by means of confocal laser scanning microscopy. The permeation time through the composite layer was of the order of 10(1)-10(2) min, while in the absence of lipids 6-CF equilibrated faster than the time resolution of the technique.