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The challenge of producing polymer vesicles remains difficult, despite numerous attempts to modulate the kinetics of polymer vesicle budding and achieve precise control over the membrane characteristics. An innovative approach that incorporates the use of copolymer-loaded single-emulsion droplets is proposed to address this challenge. This method enables the precise manipulation of micelles and polymer vesicles’ composition, structures and dimensions. The emulsion contracts and forms microspheres when the copolymer concentrations exceed > 0.5 wt%, resulting in the formation of nano polymer vesicles. Conversely, the copolymer spontaneously forms micro polymer vesicles and micelles through vesicle budding at lower concentrations. The spontaneous production of vesicles and micelles can be induced by modifying the copolymer concentration in the emulsion. Our discoveries have a significant impact relative to the development of copolymer membranes and contribute to an enhanced comprehension of the mass manufacturing of polymer vesicles from single emulsions.