AbstractA mixture of homopolymer and graft copolymer was obtained by adding the monomer at 0°C to the polylithiodiene solution. Styrene, methyl methacrylate, and acrylonitrile were used as the monomers. Polylithiodienes were prepared by the metalation of diene polymers, i.e., polybutadiene or polyisoprene, with the use ofn‐butyllithium in the presence of a tertiary amine (N,N,N′,N′‐tetramethylethylenediamine) inn‐heptane. The graft copolymers were separated by solvent extraction and were confirmed by turbidimetric titration and elementary analysis. Oxidation of the polybutadiene–styrene grafts revealed that the molecular weight of the side chains was the same as the molecular weight of the free polystyrene formed. The grafting efficiency and grafting percentage were studied for polybutadiene–styrene graft copolymers prepared under vari