Novel PCL/POE copolymers were synthesized by step growth polymerization of poly(e-caprolactone) diols and poly(ethylene glycol) diacids using dicyclohexylcarbodiimide as coupling agent. The reaction was performed at room temperature and yielded multiblock copolymers with predetermined PCL and POE block lengths. The resulting copolymers were characterized by various analytical techniques including SEC, IR, 1H NMR, DSC and X-ray diffractometry. Data showed that the properties of these polymers can be modulated by adjusting the chain lengths of the macromonomers. In particular, one or two crystalline structures can exist within the copolymers of various crystallinities.