The synthesis of specially designed chain-functionalized polystyrenes with a definite number of benzyl bromide moieties by an iterative divergent methodology is described. Such functionalized polystyrenes involve alpha,omega-chain-end-functionalized polystyrenes with benzyl bromide moieties, in-chain-functionalized polystyrenes with benzyl bromide moieties, and in-chain-functionalized polystyrenes with benzyl bromide moieties that are placed at two sites in a chain. The number of benzyl bromide moieties varied from 2 to 16 at each place. Three series of well-defined star-linear block polystyrenes of the types star-block-linear-block-star, linear-block-star-block-linear, and linear-block-star-block-linear-block-star-block-linear have been successfully synthesized by coupling these benzyl bromide-chain-functionalized polystyrenes with polystyryllithiums end-capped with 1,1-diphenylethylene.