The synthesis of well-defined chain-end-functionalized poly(methyl methacrylate)s with a definite number of benzyl bromide moieties via an iterative divergent approach starting from the living anionic polymer of methyl methacrylate is described. Only two sets of reactions involving coupling and transformation reactions are needed for the entire iterative reaction sequence. By repeating the iterative reaction sequence, chain-end-functionalized poly(methyl methacrylate)s with 2, 4, 8, and 16 benzyl bromide moieties were synthesized successfully. The resulting benzyl bromide-functionalized poly(methyl methacrylate)s underwent coupling reaction with living anionic polymers of methyl methacrylate, tert-butyl methacrylate, styrene, and isoprene to quantitatively afford well-defined regular 3-, 5-, 9-, and 17-arm star-branched poly(methyl methacrylate)s and asymmetric star-branched polymers containing poly(methyl methacrylate) segments.