In aqueous solution, poly(2-vinylpyridine-b-ethylene oxide) spontaneously forms bilayer vesicles, the size of which can be tailored by extrusion through polycarbonate membranes. However, their size can be even more precisely influenced by subjecting them to a specific cooling/warming process proceeding through a cylinder-vesicle shape transition. The thermotropic alterations of the polymer aggregates and the topological pathways of the cylinder-vesicle transition were followed by dynamic light scattering (DLS) and cryo-electron microscopy (cryo-TEM). Upon cooling the vesicles to 4degreesC, there is a transition of the vesicles to basketlike aggregates and their further disintegration to wormlike micelles. Rewarming of the dispersion results in the reformation of vesicles via intermediate discoid and octopus-like structures. The variation of incubation times at 4 and 25degreesC, heating rate, polymer concentration, and ionic strength allows tailored preparation of unilamellar and almost monodisperse vesicles with diameters between 60 and 500 nm. Furthermore, fluorescently labeled dextrans, which were used as model drugs of differing molar mass, could be easily and stably encapsulated during the thermotropic formation of vesicles from wormlike micelles.