A novel versatile light-triggered strategy is developed to organize inorganic nanoparticles (NPs) into nanovesicles with single or multiple layers in mixed solvents. This strategy constitutes a new assembly mechanism based on the photo-oxidation of thiol ligands. Compared with currently-used individual semiconductor NPs, the prepared CdSe QD vesicles exhibit an improved catalytic activity and unprecedented catalytic stability towards solar-driven hydrogen production. This light-triggered approach to functional nanoarchitectures would lead to new opportunities in various applications.