The precise synthesis of a series of exact graft polystyrenes (PS)s with two, three, four, and five branches by a new iterative methodology based on living anionic polymerization is described. The methodology involves only three reaction steps in each iterative reaction sequence, i.e., (1) a transformation reaction of the 3-(tert-butyldimethylsilyloxy)propyl (SiOP) group into 3-bromopropyl function via deprotection of the silyl group, (2) a linking reaction of alpha-SiOP-omega-1,1-diphenylethylene (DPE)-functionalized polymer anion with alpha-terminal 3-bromopropyl-functionalized PS to prepare the backbone chain with the incorporation of a DPE moiety in the chain, and (3) an addition reaction of PSLi with the DPE moiety in the backbone to introduce a PS branch. By repeating the reaction sequence five times, we have succeeded in successively synthesizing a series of exact graft (PS)s having up to five branches for the first time. In the graft (PS)s all thus synthesized, not only the molecular weights of both backbone and branch chains but also the number and position of branch chains were precisely controlled.