Self-assembly of (pyrrolyl)- and (cyclopentadithiophene-4-yl)-n-hexylferrocene on indium-tin-oxide electrodes was investigated in acetonitrile. Layers are formed from both the ferrocene and the ferrocenium forms at a rate 3 orders of magnitude higher for the latter. Oxidation of the cyclopentadithiophene heads leads to a self-assembled layer of polythiophene contacting directly the electrode surface.