LAUSR

Lipid‐like ion‐pair amphiphile vesicles, or catanionic vesicles, have emerged as potential drug carriers. The effects of cholesterol on the properties of catanionic vesicles have yet been systematically studied. Here, we compared the effects of cholesterol on the structures and fluidities of dipalmitoylphosphatidylcholine liposomes and catanionic vesicles with similar main transition temperatures (Tm). For liposomes, fluorescence anisotropy (FA) thermograms reveal typical condensing and disordering effects of cholesterol above and below Tm respectively. In contrast, FA and molecular simulation data reveal that catanionic bilayers below Tm are more fluidic due to shorter alkyl chains. This leads to only condensing effects of cholesterol for catanionic vesicles at all temperatures. Our results provide important insights into the fabrication of catanionic vesicles as novel drug carriers.