A hexaarm hexachloropolystyrene star polymer 1 ( n= 18 000 g mol–1) is functionalized by reaction with Me3SiN3 to give the hexaazido star polymer 2; reduction of 2 by PPh3/H2O leads to the hexaamine star polymer 3, and reaction of 2 with a two-fold excess of C60 gives the hexafullerence star polymer 4, characterized by size-exclusion chromatography, NMR, thermal-gravimetry analysis and CV.