A facile route to synthesize well‐defined polybutadiene (PBd) DendriMacs is described. In a highly modified approach to that recently published for the synthesis of polystyrene DendriMacs, a G1 polybutadiene (PBd) DendriMac has been synthesized in three simple and high yielding steps. The first step involves the synthesis of a three‐arm PBd mikto arm star in which one arm has a terminal hydroxy group introduced by the use of a protected functionalized initiator. Following fractionation of the star, the hydroxy group is deprotected and converted into an alkyl bromide moiety before coupling the star to a trifunctional core (1,1,1‐tris(4‐hydroxylphenyl)ethane) by a Williamson coupling reaction catalyzed by cesium carbonate to yield a G1 PBd DendriMac.
