Functionalized branched polysiloxanes with star-branched, comb-branched and dendritic-branched topologies were synthesized. The branched macromolecules were generated by coupling of reactive blocks using a grafting technique (ACS Polym. Prepr. 2001, 42, 227; ACS Symp. Ser. 2003, 838, Chapter 2). The living anionic ring-opening polymerization (ROP) of vinyl-substituted cyclotrisiloxanes (ViMeSiO)(3), V-3, and, ViMeSiO(SiMe2O)(2), VD2, and the copolymerization of these monomers with hexamethylcyclotrisiloxane, D-3, was explored to obtain reactive blocks. Termination of the living polymer, having a lithium silanolate end group, on a reactive core containing SiCl groups led to the grafting of living polysiloxane on the core. Transformation of vinyl groups in the polymer into the reactive SiCl groups by hydrosilylation with Me2HSiCl made possible the grafting of a successive generation of branches. The reactive blocks of high and low density of the precursor vinyl group were obtained by the polymerization of monomers V-3 and VD2, respectively. While the homopolymerization led to a uniform density of vinyl groups along the chain, the copolymerization of V-3 or VD2 with D-3 produced a gradient distribution with the density decreasing in the direction of the chain growth. This arrangement led to a higher density of the vinyl group in the external part of the branched macromolecule. Study of kinetics of the copolymerization Of V-3 with D-3 in THF initiated by BuLi gave the reactivity coefficients k(v3) = 17.8, k(D3) = 0.036 (25 degreesC), from which the density distribution of vinyl groups in reactive blocks may be determined. Four-arm star copolymers were obtained using (MeCl2SiCH2)(2) as the core, whereas the comblike polysiloxane was obtained from a linear copolymer of ViMeSiO and Me2SiO treated with Me2HSiCl. Dendritic polysiloxanes of the first and second generation were obtained using the functionalized starlike polysiloxane as the core.