The assembly of amphiphilic block copolymers in well-defined polymer nanoparticles is an intricate interplay between polymer composition, method of assembly and the properties of the organic solvent used to dissolve the polymer building blocks. Remarkably, the role of organic solvent composition has been much less studied in comparison to the other two parameters. Here we have systematically investigated the effect of organic solvent composition, namely, the ratio between tetrahydrofuran and dioxane, on the self-assembly of PEG-PDLLA copolymers into polymer vesicles and their subsequent shape change in different topologies. Uncovering such physical basis unlocks new opportunities for the development of complex nanoparticles without the need of extended polymer engineering processes.
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