Dielectric relaxation spectroscopy was used to investigate the molecular dynamics of model segmented polyurethane copolymers having identical hard segments and hard segment weight fractions, but with four different soft segment chemistries of particular interest in biomedical devices. All soft segments have molecular weight similar to 1000 g/mol and are composed of either tetramethylene oxide, hexamethylene oxide, aliphatic carbonate, or dimethylsiloxane (PDMS) segments. These microphase-separated materials exhibit rich dielectric relaxation behavior: up to two relaxations in the glassy state, a segmental alpha relaxation (two for the polymer with predominately PDMS soft segments), and three slower relaxations. The slowest process arises from interfacial (MWS) polarization, and its strength decreases significantly with increasing temperature (over a few tens of degrees) and disappears at a temperature similar to that at which the small-angle X-ray scattering from the phase-separated microstructure disappears.