A polyisoprene-block-poly(2-cinnamoyethyl methacrylate) (PI-b-PCEMA) sample with a narrow molar mass distribution was prepared and characterized. The sample formed spherical micelles in hexanes/THF with 20% of THF by volume. After photo-cross-linking of the PCEMA care took place, the PI corona block was cleft by ozone and (CH3)(3)P treatment to produce PCEMA nanospheres with surface carbonyl groups or PCEMA-CO nanospheres. These spheres were stable without any added surfactant in a good solvent for PCEMA. Reaction of the carbonyl groups with cyclopentadiene catalyzed by pyrrolidine yielded fulvene-covered nanospheres, PCEMA-FV nanospheres, which possessed better solubility in organic solvents than the PCEMA-CO spheres. This work represents the first attempt at the preparation of cross-linked nanospheres with immediately attached surface functional groups from block copolymers. When appropriately functionalized, these nanospheres should be useful as solid lubricant or support for catalysts.