Block copolymers have been used to tune the chemical and physical properties of degradable materials for tissue engineering. In this study, a series of urethane linkages containing segmented poly-ε-caprolactone (sPCL) with various block lengths and weight ratios were synthesized and characterized. The molecular conformations and characteristics of sPCL were investigated using nuclear magnetic resonance, Fourier transform-infrared spectroscopy, and gel permeation chromatography. The effects of the molar ratio and molecular weight of ε-caprolactone precursors on the mechanical properties were studied. The results show that the tensile strength of sPCL, which is tunable, was 35 MPa, much higher than that of a typical PCL sample (16 MPa). In addition, it was found that increasing the number of urethane linkages improves elongation. In vitro studies confirmed that the change of molecular weight of sPCL was significantly accelerated compared to that of homopolymers. These results suggest that sPCL has potential as a tailorable material for implantable devices.