The self-assembly of shape amphiphiles that was created by covalently tethering spherical nanoclusters and polymers has produced various aggregates such as spherical and cylindrical micelles and vesicles. However, mechanistic studies on the self-assembly of polyoxometalate-polymer hybrids are very limited. Here, we extend our previous work for better understanding of the concentration-induced self-assembly of a polyoxometalate-polystyrene (POM-PS) hybrid upon POM cluster protonation. By controlling the concentration, we could observe various morphologies from single molecules to micelles, compound micelles, spherical vesicles, cylindrical vesicles, and finally, large vesicles. These findings further deepen our mechanistic understanding of the self-assembly of the protonated hybrid, and will facilitate the development of aggregates that contain the protonated POM clusters with well-controlled structures and optimised functionality for future value-added applications.