The surface of sonicated suspensions of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) in water was studied by means of X-ray-reflectivity measurements as a function of temperature and time. This revealed the generation of a surface-confined stack of bilayers beneath the monolayer at the air-suspension interface at 29 ° C. Further experiments at different temperatures have shown that this temperature is optimal for the growth of such novel structures. The evolution of multiple bilayers persists for more than 15 h after creation of the monolayer. The bilayer repeat distance of 6.22 nm corresponds to the previously measured value pertaining to the fully hydrated DMPC bilayer membranes. It is inferred that the development of surface-associated multibilayers involves partial lipid dehydration near the water surface and subsequent enforced vesicle fusion into the surface-aligned lipid bilayer membranes. Detailed analysis of the X-ray-reflectivity data reveals decreasing lamellar order with distance from the covering monolayer. The number of adsorbed bilayers increases with time, finally reaching the value of eight. The interbilayer repeat distance changes gradually from 6.22 nm at temperatures higher than 27°C to 6.45 nm at temperatures lower than 24°C. This is indicative of the surface-affected L~ La phase transition. The mean temperature of this transition T~rfac¢ = 26.5°C is significantly higher than that measured with the same DMPC suspension in the bulk (Tin = 23.5°C), possibly due to the partial bilayer dehydration in the proximity of the surface.