Carbosilane dendrimers adorned with either triarylamine or carbazole units in their periphery exhibit novel electrochemical behavior in which the electrochemical deposition is controlled by dendrite generation. In addition, the deposited layers remained intact in the depositing solvent, methylene chloride, allowing a second layer to be deposited on top of the first layer. We have sought to establish the suitability of this electrochemical deposition technique for use in the construction of multi-layer OLEDs, which cannot be fabricated via conventional spin-coating with a polymeric precursor. Thus, the electrochemical deposition-based process could potentially offer an ideal combination of deposition control on the one hand and multi-layer fabrication on the other. We report herein the novel electrochemical deposition behavior of arylamine or carbazole end-capped carbosilane dendrimers of the type GnNPB or GnCBP (n = 1-4) and their use for the formation of multi-layer devices for OLEDs.