The templated electrochemical growth of poly(3,4-ethylenedioxythiophene) (PEDOT) into porous sol-gel (PSG) films and PEDOT-mediated electron transfer to ferrocene-modified dendrimers encapsulated within these sol-gel matrices, were analyzed. The conditions needed to optimize PEDOT electropolymerization within the PSG films such that barely emergent PEDOT features protrude from a PSG thin film surface, were also described. It was observed that oxidation/reduction of the encapsulated Fc-PAMAM units could be voltammetrically detected after PEDOT growth into the sol-gel film. The results show that up to ca. 20% of these Fc-PAMAM units became electrochemically active, with high rates of electron transfer, when EDTM was conjugated to the Fc-PAMAM dendrimer.