PACS. 87.16.Dg -First pacs description. PACS. 87.15.He -Second pacs description. PACS. 61.10.Eq -Third pacs description.Abstract. -The hydration process of multi-stacked phospholipid bilayers to form giant vesicles was investigated by time-resolved small angle X-ray scattering. The hydration of lipids in the liquid-crystalline phase was found to proceed in two stages. In the early stage, until about 100 s after hydration, lipid bilayers on a solid substrate swell about 12Å and reach a quasi-stable state. In the late stage, after several hundreds of seconds, lipid bilayers gradually peel off from the stack. On the other hand, in the case of a lipid in the gel phase, only the early stage is observed. These behaviors correspond to the capacity for the giant vesicle formation depending on the lipid phases. The kinetics of the peeling-off process is discussed in terms of Kramers' formulas.c EDP Sciences