Electrochemically active polyurethanes containing ferrocene units in hard segments (PU-H-Fc) have been synthesized and identified by H-1-NMR spectra. Electrochemical properties of PU-H-Fc blending with lithium perchlorates were investigated by cyclic voltammetry (CV) and compared with that of polyurethane with ferrocene units in polyether soft segments (PU-S-Fc) and of ordinary polyurethane blending with ferrocene (PU-B-Fc). The apparent formal potentials were found to be similar. The results illustrated that the original redox property of ferrocene was maintained when it was covalently linked to the hard segment as well as to the soft polyether main chain. The peak separation in PU-S-Fc was much greater than in PU-H-Fc, demonstrating that the softness and flexibility of the PEO chain was maintained by fixing the redox units on the hard segments instead of on the soft segments, and the diffusion rate of redox units was increased because the migration of the active substance was enforced by the motion of the polymer chain. The peak position and peak separation of PU-H-Fe were similar to those of ordinary polyurethane blending with ferrocene. In the PU-H-Fc system the physical loss of admix redox molecules by migration can be avoided and the diffusion rate of redox units maintained. This is highly desirable in many electrochemical systems.