Di-block copolymers composed of two biocompatible polymers, poly(ethylene glycol) and poly(D,L-lactide), were synthesized by ring-opening polymerization for preparing polymer vesicles (polymersomes). Emulsion solvent evaporation method was used to fabricate the polymersomes. Scanning electron microscope (SEM) images confirmed that polymersomes have a hollow structure inside. Confocal laser microscope and optical microscope were also used to verify the hollow structure of polymersomes. Polymersomes having various sizes from several hundred nanometers to a few micrometers were fabricated. The size of the polymersomes could be readily controlled by altering the relative hydrodynamic volume fraction ratio between hydrophilic and hydrophobic blocks in the copolymer structure, and by varying the fabrication methods. They showed greatly enhanced stability with increased molecular weight of PEG. They maintained their physical and chemical structural integrities after repeated cycles of centrifugation/re-dispersion, and even after treatment with surfactants.