Anionic polymerization techniques utilizing 1,2,4,5-tetra(bromomethyl)benzene as the linking agent were employed for the synthesis of four-arm star polymers with poly(tert-butyl methacrylate) (PtBuMA), poly(methyl methacrylate), poly(tert-butylacrylate) (PtBuA), or poly(2-vinylpyridine) (P2VP) branches. This work was extended through the "grafting onto" method, in combination with anionic polymerization techniques, to synthesize graft copolymers consisting of polystyrene backbones and PtBuA, PtBuMA, or P2VP branches. Postpolymerization reactions were performed to produce graft copolymers with polyelectrolyte branches. Crosslinking reactions were observed in some of the graft materials several months after their preparation.