In this study, the synthesis, structure and physical properties of two series of thermoplastic polyurethanes based on hydroxypropyl-terminated poly-(dimethylsiloxane) (HP-PDMS) or hydroxyethoxypropyl-terminated poly-(dimethylsiloxane) (EO-PDMS) as soft segments, and 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as hard segments were investigated. The poly-urethanes were synthesized by two-step polyaddition in solution. The effects of the type and content of PDMS segments on the structure, thermal and surface properties of copolymers were studied by 1 H-, 13 C-nuclear magnetic resonance (NMR) spectroscopy and two-dimensional NMR spectroscopies (heteronuclear multiple bond correlation (HMBC) and rotating-frame nuclear Overhauser effect (ROESY)), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide-angle X-ray scat-tering (WAXS), scanning electron microscopy (SEM) and water contact angle and water absorption measurements. Thermal properties investigated by DSC indicated that the presence of soft PDMS segments lowers the glass transition and melting temperatures of the hard phase as well as the degree of crys-tallinity. SEM analysis of the copolymers with a lower soft segment content confirmed the presence of spherulite superstructures, which arise from the crystallization of the hard segments. When compared with polyurethanes prepared from HP-PDMS, the copolymers synthesized from EO-PDMS with the same content of the soft segments had a higher degree of crystallinity, better thermal stability and a less hydrophobic surface. The obtained results showed that the synthesized polyurethanes had good thermal and surface