Segmented poly(ester-urethanes) (PEUs) based on poly(epsilon-caprolactone) (PCL) as a soft segment and a non-aromatic diisocyanate in the hard segment were synthesized. The soft segment crystallinity and other physical properties of the PEUs were studied. It was found that the crystallinity and rate of crystallization of the PCL continuous phase in the PEUs decreases and the glass transition temperature of PEUs increases in comparison with the PCL prepolymers. The restriction of the crystallization of the PCL soft segment depends on the hard segment concentration, length of the soft segment, and total molecular weight of the PEUs.