End-capped triarylamine and carbazole dendrimers were prepared through the divergent synthesis based on the reaction of diethenyl propagating carbosilane dendrimers with suitable functional groups such as the naphthylphenylaminophenyl (NPB) or carbazolylphenyl (CBP) unit. The electrochemical deposition behavior in higher generation dendrimer was observed in cyclovoltammetric experiments, leading to the good film formation on ITO. The deposited films remained intact in the depositing solvent and the film thickness was adjusted by varying the number of CV cycles. To obtain the reason of this behavior, the electrochemical property of compounds based on silicon (Me4·nSi(CBP) n) was systematically studied. Moreover, multi-layer films could be fabricated without causing any damage to the previous layer. To this ends, the fabrication of OLEDs using this electrochemical deposition process was also investigated.