The biodegradable polyetheresteramide-based polyurethane (PEEA-U) copolymers were prepared by melt polycondensation method from ε-caprolactone, 6-aminocaproic acid, poly(ethylene glycol), and toluene diisocyanate (TDI). The polymers were characterized by1H-NMR, FTIR, and the thermal properties were studied by DSC and TGA/DTG analysis. With the addition of TDI, the melting temperature and the enthalpy increased . The hydrolytic degradation behavior of these copolymers were also studied.The results showed that with the decrease of the pH from 9.10 to 4.02, the degradation rate increases rapidly, and the degradation rate of the PEEA-U-E is slower than that of PEEA-U-0, which might be due to the difference in the macromolecular weight and the crystallinity of the copolymers.