A series of [60]fullerene (C₆₀)-containing poly(ethylene oxide)-block-polystyrene (PEO-b-PS) with various numbers and different locations of C₆₀ along the polymer chains were designed and synthesized via a combination of “click” chemistry and living/controlled polymerization techniques such as anionic polymerization, atom transfer radical polymerization, and reversible addition–fragmentation chain transfer polymerization. One C₆₀ was tethered either to the end of a PS block (PEO-b-PS-C₆₀) or at the junction point between PS and PEO blocks [PEO-(C₆₀)-PS]; while multiple C₆₀s could be attached randomly along the PS block (PEO-b-PS/C₆₀). The reaction conditions were carefully controlled to ensure a quantitative C₆₀ functionality at precise locations in the case of PEO-b-PS-C₆₀ and PEO-(C₆₀)-PS and to avoid crosslinking in the synthesis of PEO-b-PS/C₆₀. The results have implications in the precision synthesis of fullerenepolymers in general. These C₆₀-containing diblock copolymers possess different composition, diverse architecture, and high fullerene functionality. They can serve as model “shape amphiphiles” for the construction of complex hierarchical structures via the interplay between C₆₀–C₆₀ aggregation and block copolymerself-assembly/micro-phase separation.