A series of multiarmed and multicomponent miktoarm (μ‐) star polymers have been successfully synthesized by developing a new iterative methodology based on a specially designed linking reaction of the block copolymer in‐chain anions, whose anions are positioned between the blocks, with α‐phenylacrylate (PA)‐functionalized polymers. The iterative methodology involves the following two reaction steps: a) introduction of two different polymer segments by the linking reaction of a block copolymer in‐chain anion with a PA‐functionalized polymer and b) regeneration of the PA reaction site. By repeating this reaction sequence, two different polymer segments are advantageously and successively introduced into the μ‐star polymer. In practice, repetition of the reaction sequence affords well‐defined 3‐arm ABC, 5‐arm ABCDE, 7‐arm ABCDEFG, and even 9‐arm ABCDEFGHI μ‐star polymers, composed of polystyrene, polystyrenes substituted with functional groups, polyisoprene, and poly(alkyl methacrylate) arms, respectively. image