Stryrenic macromonomers of polybutadienes (sMMB) were synthesized by selective reaction of living polybutadienes with the silyl chloride group of 4-(chlorodimethylsilyl)styrene, Anionic copolymerization of sMMBs with butadiene, in the presence of a randomizer (potassium 2,3-dimethyl-3-pentoxide randomizer), led to living random comb polybutadienes (PBCs). Taking advantage of the living character of the PBCs, a number of well-defined comb, star-comb, and comb-on-comb polybutadienes were synthesized by using high-vacuum techniques. All samples prepared were characterized by size exclusion chromatography (SEC) with DRI detector and SEC with two-angle laser light scattering detector (SEC-TALLS).