[60]Fullerene (C-60) was mono-substituted with well-defined poly(methyl methacrylate) (PMMA-b-C-60) using the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviors of PMMA-b-C-60 in ethyl acetate (EA) and decalin mixtures were studied using laser light scattering (LLS) and transmission electron microscopy (TEM). Homogeneous solutions of PMMA-b-C-60 can be obtained in the solvent mixtures containing more than 40 wt% EA, where the molar ratio of decalin to EA is close to 1. For each solvent mixture, unimers coexist with micelles and large aggregates. The sizes of PMMA-b-C-60 micelles and aggregates are independent of polymer concentration, confirming that they are produced via the closed association mechanism. For the various solvent mixtures, the weight-averaged molecular weights, M, of the PMMA-b-C-60 aggregates range from 4.1 x 10(7) to 12.5 x 10(7) g/mol. The hydrodynamic radii of the large aggregate, Rh, vary from 90 to 136 nm, while the z-averaged radii of gyration, R-g, range from 210 to 311 nm. The R-g/R-h value for each solvent mixture is similar to 2.3, which is independent of decalin contents in the mixed solvents. The morphological study using the transmission electron microscope suggests that the large aggregates are composed of porous large compound micelles (LCM) in solution. (c) 2005 Elsevier Ltd. All rights reserved.