Double-layered dendritic carbosilanes were prepared containing phenylethynyl groups on the peripheral layer as well as propyleneoxy and ethenyl groups in the inner shell. The preparation of the allyloxy group containing dendrimers was made by the reaction of chlorosilylated dendrimers with allylalcohol in the presence of TMED. The dendrimers with ethynyl groups on each terminal arm were obtained by the reaction of the chlorosilyl group containing generations with lithium phenylethynyl. Subsequently, by iterative reactions such as hydrosilation and alkynylation as well as alcoholysis, dendritic macromolecules were generated to the fourth generation with 64 phenylethynyl groups on the peripheral layer. Different branching layers such as propyleneoxy and phenylethenyl groups constructed the inner shell of the fourth generation of the prepared dendrimers. The dendrimers were characterized by the use of nuclear magnetic resonance, infrared, size exclusion chromatography, differential scanning calorimetry, ultraviolet, and elemental analysis.