Gels from diacylphosphatidylcholine in glycerol/butylene glycol mixtures were investigated by pulsed-field gradient NMR measurements. Previous measurements had shown that the gels are formed by networks from crystalline multilamellar vesicles (MLV). The obtained self-diffusion coefficients for water and butylene glycol molecules indicate that both molecules occur in two different environments, even at temperatures above the phase transition T(m) where the system is still in a liquid crystalline state. While the larger fraction of the molecules shows a free self-diffusion process like in a homogeneous phase, the smaller fraction seems to be encapsulated in closed domains and undergoes only hindered self-diffusion. It is concluded that the hindered diffusions are due to the solvent molecules trapped between the bilayers of the multilamellar vesicles, while the free diffusion is assigned to the solvent molecules outside of the MLV. Since the fraction of the entrapped molecules does not change during phase transition, we assume that the structure of the network in the samples remains the same when gelation occurs. The gelation process is simply due to the transformation of the vesicle bilayers from the liquid crystalline to the crystalline state. The permeability of the bilayer for the solvent molecules is drastically changed by this transition. The exchange of water molecules through the bilayers slows down significantly below T(m): while the average residence time of water molecules inside the vesicles is smaller than 50 ms in the liquid crystalline state, this value increases to more than 1 s for the gel state. In the case of pure butylene glycol, no vesicles are present, and it is likely that these gels are formed from crystalline fibers.