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These vesicles can be designed for inherent or selective permeability through the choice of suitable copolymers or the incorporation of protein nanopores, respectively. In this study, we explore a novel approach using oxygen\u2010producing enzymatic reactions within biodegradable poly(ethylene glycol)\u2010poly(caprolactone\u2010gradient\u2010trimethylene carbonate) (PEG\u2010p(CL\u2010g\u2010TMC)) polymersomes to modulate drug release. These polymersomes were found to enhance the release of hydrophobic drugs while retaining hydrophilic drugs. The enzymatic generation of oxygen within the polymersomes increased membrane hydrophobicity, influencing drug release kinetics. 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