A well-defined amphiphilic block copolymer bearing a reactive azide group at the interface of two blocks, poly(ethylene oxide) (-azido)-block-polystyrene (PEO(-N-3)-b-PS), has been successfully synthesized via a combination of end group transformation and atom transfer radical polymerization (ATRP). The subsequent [3 + 2] cycloaddition reaction between PEO(-N3)-b-PS and C-60 led to the facile preparation of PEO(-C-60)-b-PS, in which a single C-60 moiety was located at the diblock junction point. Fullerene-containing hybrid vesicles were then fabricated for the first time via the supramolecular self-assembly of PEO45(-C-60)-b-PS380 in aqueous solution using 1,4-dioxane as the cosolvent. The current example augurs well for tunable spatial ordering of desired moieties (fullerene or other functional nanoparticles) by employing block copolymers as self-organizing templates.