Sulfur containing graft polymers that may be of interest as polymeric transfer agents were synthesized. Graft polymerization of propylene sulfide on crosslinked polystyrene beads was investigated; both crosslinked polystyrene and its chloromethylated derivative were grafted. Crosslinked polystyrene was metallated by BuLi–TMEDA and was used to initiate anionic graft polymerization of propylene sulfide. Graft polymers of high polypropylene sulfide content corresponding to 10 mmol s/g were obtained. The grafted polypropylene sulfide was evenly distributed across the bead cross section. No change in bead surface characteristics was observed. Grafting on chloromethylated polystyrene beads was achieved by reaction between the chloromethylene groups with sulfide groups of performed polypropylene sulfide, and with terminal sodium thiolate groups of living polypropylene sulfide.