Synthesis Of 2(nd) generation dendritic polymeric materials via anionic polymerization procedures in combination with chlorosilane chemistry, consisting either from one polydienic segment (homopolymers) or from two chemically different polydienic components (copolymers), is described. The polydienes used were poly(butadiene) (PB) with similar to 90% 14-isomerism and poly(isoprene) (PI) with increased 3,4-isomerism (similar to 60%). Molecular characterization of intermediate products and the final dendritic materials was made with Gel Permeation Chromatography (GPC), Membrane and Vapour Pressure Osmometry (Mo and VPO respectively), Gas Chromatography -Mass Spectroscopy (GC-MS) and H-1-Nuclear Magnetic Resonance (H-1-NMR) Spectroscopy, leading to the conclusion that they can be considered model polymers. morphological studies solely with Transmission Electron Microscopy (TEM) have been conducted on two of the four synthesized copolymer samples exhibiting microphase separation between the two polydiene segments.