The grafting reaction of poly(1,3-cyclohexadienyl)lithium onto fullerene-C-60 (C-60) was strongly affected by the nucleophilicity of poly(1,3-cyclohexadiene) (PCHD) carbanions and the polymer chain microstructure, and progressed via step-by-step reactions. A star-shaped PCHD, having a maximum of four arms, was obtained from poly(1,3-cyclohexadienyl)lithium composed of all 1,4-cyclohexadiene (1,4-CHD) units. The rate of the grafting reaction was accelerated by the addition of amine. The grafting density of PCHD arms onto C-60 decreased with an increase in the molar ratio of 1,2-cyclohexadiene (1,2-CHD) units. The electron-transfer reaction from PCHD carbanions to C-60 did not occur in either a nonpolar solvent or a polar solvent. (C) 2008 Wiley Periodicals, Inc.