The role of a new class of oxidative-responsive polymeric vesicles that could be applied as nanocontainers in drug delivery, biosensing and biodetection was discussed. It was observed that the synthetic path was based on the anionic ring-opening polymerization of episulfides, initiated by a thiolate group. It was also found that the oxidation sensitivity of the vesicles were investigated by turbidimetry. Vesicle degradation was investigated when the oxidative environment was generated by the system glucose-oxidase (Gox)/glucose/O 2. A 1H nuclear magnetic resonance (NMR) spectroscopy of the polymersome suspensions was also employed before, during and after oxidation to characterize the nature of the observed morphological changes.