Poly(ferrocenyldimethylsilanes) with different molecular weights, especially with high molecular weight, have been synthesized. It is found by using the ESR technique that the formation of charge transfer complexes (CTC) between poly(ferrocenyldimethylsilanes) with different molecular weights and tetracyanoethylene (TCNE) is possible. Using 2,2,6,6-Tetramethyl-piperidone-1 as a spin probe, the segment motion of resultant polymers was investigated.