The phase behavior of mixtures of a vesicle-forming copolymer and related to it copolymers of different phase propensities was studied by light scattering and cryogenic transmission electron microscopy. The vesicle-forming copolymer and the copolymeric additives are based on poly(ethylene glycol) (PEG) and comprise from 1 to 8 lipophilic lipid-mimetic anchors which form hydrophobic moieties. The ability of the additives to control the vesicle size and particle morphology was examined as a function of their content, composition, and phase propensity. At the lower guest to host molar ratios, the bilayer organization is preserved and changes in the vesicle dimensions are not observed. At a certain ratio which is dependent on the composition and phase propensity of the guest copolymer the particle dimensions start to change, and typically, transitions from low-to high-curvature structures are observed. The critical value of the mean PEG interfacial area at which the particles undergo size, size distribution, and phase transitions slightly depends on the composition of the guest copolymer and is found to be roughly 3 nm.(2)