Novel star‐shaped polymers with various stereo‐regular arm polymers are synthesized by a combination of stereospecific living anionic polymerization and transition metal‐catalyzed radical linking polymerization, in which the terminal halogen mediates the transformation of the growing active species from a carbanion into a carbon radical. Using this technique, a series of star polymers with isotactic and syndiotactic poly (methyl methacrylate) arms can be prepared with various stereocomplexation behaviors.