Addition of bulky C-60 moiety, a powerful electron acceptor (EA = 2.6-2.8 eV), to the poly(p-bromostyrene) (PBS) by a novel organometallic reaction considerably changes the chemical and physical properties of this polymer. The product obtained is a "charm-bracelet" non-crosslinked brownish yellow polymer which is easily soluble in many common organic solvents, and has a single glass transition temperature [134.0 degrees C vs. 83.2 degrees C for poly(p-bromostyrene)], this being congruent with its chemical structure. Covalent attachment of C-60 to the brominated polystyrene backbone is confirmed by a variety of techniques such as UV-VIS, FT-IR, TGA, DSC, SEM, ESR, GPC, and C-13-NMR. The results show that both the stereo-electronic effect and the steric hindrance of C-60 have an important influence on the structure and physical properties of polymer.