In this paper, a new kind of biodegradable aliphatic polyetheresteramide copolymers (PEEA) based on epsilon-caprolactone, 6-aminocaproic acid, and poly(ethylene glycol) (PEG) were synthesized by melt polymerization method. The obtained copolymers were characterized by 1H-NMR. The thermal properties of PEEA copolymers were studied by DSC and TGA/DTA under nitrogen atmosphere. The water absorption and hydrolytic degradation behavior was also studied in detail. With the increase in PEG content or the decrease in caprolactone content, the water absorption of the copolymers increased accordingly. For the hydrolytic degradation behavior, with the increase in PEG content or caprolactone content, the degradation rate increased then.