Novel highly functionalized polysiloxanes have been synthesized, which bear small pendant dendritic wedges containing two different redox-active organometallic moieties, namely the electron-donating ferrocenyl group and the electron withdrawing (eta(6)-aryl)tricarbonylchromium entity. Hydrosilylations of vinylsilyl-functionalized (CH2=CH)MePhSiFc (1) and allyisilyl-terminated dendron (CH2=CHCH2)PhSi[CH2)(2)MePhSiFc](2) (3), with the Si-H-containing polysiloxane backbones (Me3SiO)(MeSiHO)(n)-(Me2SiO)(m)(SiMe3) (n = 30-35%, m = 65-70%), and (Me3SiO)(MeSiHO)(n)(SiMe3) (n similar to 35) successfully afforded the novel siloxane-based copolymers 8 and 9 and homopolysiloxanes 10 and 11 possessing appended organometallic dendritic side chains. Thermal treatment of 8 with Cr(CO)(6) and reaction of 10 with (CH3CN)(3)Cr(CO)(3) further increased metal density of the polymers affording polysiloxanes 12 and 13 carrying (eta(5)-C5H4)Fe(eta(5)-C5H5) and (eta(5)-C6H5)Fe(eta(5)-C5H5) moieties hanging from their polysiloxane chain. Similar reactions, starting from 1,1,3,3-tetramethyldisiloxane and phenyltris(dimethylsiloxy)silane, were also a convenient way to prepare the corresponding homo and heterometallic model compounds [MePhFcSi(CH2)(2)Me2Si](2)O (5), [{eta(6)-C6H5)Cr(CO)(3)}MeFcSi(CH2)(2)Me2Si](2)O (6), and PhSi[OMe2Si(CH2)(2)MePhSiFc](3) (7). These model compounds and the metallopolysiloxanes were characterized by IR, multinuclear NMR spectroscopies and mass spectrometry. Thermogravimetric analysis (TGA) established that dendronized polysiloxanes 9 and 11, with ferrocenyl dendrons derived from 3, possess higher thermal stability than parent ferrocenyl polysiloxanes 8 and 10. Ferrocenyl dendronized polysiloxanes 9 and 11 yield ceramic products, which have been characterized by SEM and EDX microanalyses. Solution electrochemical studies showed that all the ferrocenyl units present in polysiloxanes 8-13 are electrochemically independent. Ferrocenyl polysiloxanes 8-11, deposited electroactive films onto electrode surfaces. Their well-defined and persistent redox waves are characteristic of electrochemically stable, surface-confined reversible redox couples.