We recently achieved quantitative synthesis of an amphiphilic coil-rod-coil triblock copolymer, poly(2-vinylpyridine)-b-poly(n-hexyl isocyanate)-b-poly(2-vinylpyridine), by coupling in situ living diblock copolymer poly(2-vinylpyridine)-b-poly(n-hexyl isocyanate) (P2VP-b-PHIC) using malonyl chloride in the presence of pyridine. This led to the introduction of an active methylene group that is a site for further functionalization in the rod block. The Michael addition reaction of the triblock copolymer with 7-(4-trifluoromethyl) coumarin acrylamide led to copolymer bearing a fluorescent pendent in the rod block. The fluorescent labeled copolymers were isolated in similar to 94% yields. Similarly C-60 pendent was introduced to the rod block by the Bingel reaction. The yields of C-60 functionalized copolymers were similar to 54%. The precursor and functionalized amphiphilic coil-rod-coil copolymer show diverse morphologies, such as micelles and vesicles by simply changing the solvent. For the C-60 functionalized block copolymer, structural constraints in micelles and vesicles prevented C-60 pendents to aggregate. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.