The synthesis of second-generation (G-2) dendritic polymers of isoprene (I) and styrene (S) was achieved with anionic polymerization high-vacuum techniques and by performing the following steps: (1) selective reaction of a living chain with the chlorosilane group of 4-(chlorodimethylsilyl)styrene (a dual-functionality compound) to produce a macromonomer, (2) addition of a second living chain (same or different) to the double bond of the macromonomer, (3) polymerization of I with the anionic sites, and (4) reaction of the produced off-center living species with trichloromethyl silane or tetrachlorosilane (CH3SiCl3 or SiCl4). The combined characterization results showed that the G-2 dendritic macromolecules synthesized-(S2I)(3), (SI'I)(3), (I"I'I)(3), (I'I-2)(4)-have a high molecular and compositional homogeneity.