A double-tailed surfactant, for example, dioctadecyldimethylammonium bromide (DODAB), tends to form bilayer fragments rather than vesicles in aqueous Solution upon sonication. This Letter reports on the morphological transformations of the membrane fragments leading to multilamellar vesicle formation. The surfactant membranes were swollen with tetra(11-methoxy-11-oxoundecyl)tetramethylcyclotetrasiloxane (3) (a cyclosiloxane with covalently attached fatty-acid esters) LIP to 50 mol % based oil the surfactant content. That compound was synthesized by hydrosilylation of 1,3,5,7-tetramethylcyclotetrasiloxane with four molecules of methyl undec-10-enoate. Using cryo-transmission electron microscopy (cryo-TEM), it has been shown that densely stacked multilamellar vesicles Form spontaneously in the sonicated DODAB dispersion containing 50 mol %, of the compound 3 after adjusting pH to the value of 9.5. This occurs as I result of the hydrolysis of ester bonds of the compound 3 inside the membrane with formation of tetra(11-carboxyundecyl)tetramethylcyclotetrasiloxane (4). The carboxylic groups in compound 4 are ionized under experimental conditions. That results in the appearance of the negative charge at the surface which neutralizes the positively charged molecules of DODAB, thus reducing repulsive interactions between the membrane fragments. Additionally, its was shown using Langmuir monolayer measurement, the presence of compound 4 expands the DODAB film and decreases its bending rigidity. That makes the bending process considerably easier and promotes formation of multilamellar vesicles.