The influence of the physicochemical properties of the vesicular bilayer on the sorption of poorly water soluble compounds was investigated with pulsed field gradient 1H nuclear magnetic resonance (PFG-NMR) for the case of phosphatidylcholine and dioctadecyldimethylammonium bromide (DODAB), using 4-ethylbenzyl alcohol as a model compound. Hereby, the effect of bilayer thickness at a constant physicochemical state was studied using a range of phosphatidylcholines of varying chain lengths, whereas DODAB was preferred to check the influence of the bilayer physicochemical state since this cationic lipid is characterized by three different states within the studied temperature range. When the phospholipid alkyl chain length was changed, no differences were observed in the sorption which was linked to the surface-mediated sorption. On the other hand, when the chemical composition was preserved but the temperature and thus the physical state of the bilayer were changed, the sorption in dioctadecyldimethylammonium bromide (DODAB) vesicles changed dramatically. From those experiments, a strong relationship between the ordering of the surfactant molecules and the sorption can be assumed.