The present study describes a series of novel polycarbonate urethane films that were fabricated via the solution-casting method from 4,4'-methylenebis(cyclohexyl isocyanate) (H12MDI) and 1,4-butanediol (BDO) chain extender as hard segments, poly(1,6-hexanediol)carbonate diols (PCDL) and hydroxyl-terminated polydimethylsiloxane (PDMS) as soft segments, with dibutyltin dilaurate as the catalyst. Varied molar ratios of PDMS (less than 30%) were utilized to enhance the mechanical properties and biocompatibilities. The microstructure and degrees of phase separation were characterized using atomic force microscopy. The chemical structure and surface morphology of the materials were further confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, 1H NMR and 13C NMR, water droplet contact angle and scanning electron microscopy. Thermal properties were measured by differential scanning calorimetry. MTT assay and hemolytic tests were studied for evaluating cellular viability and hemocompatibility of fabricated films using L929 fibroblast cells and adult rabbit blood. The results demonstrated polyurethane films with soft segments partially replaced by PDMS could remarkably improve the biocompatibility while maintaining relatively stable mechanical behavior, making them exciting potential candidates for artificial vessels or other tissue engineering applications.