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Poly(ε-caprolactone) (PCL) with different molecular weights was synthesized and characterized by a gel permeation chromatograph equipped with multiple detector. The melting behavior of PCL was also studied. It was found that the equilibrium melting points (Tm0) of PCL samples depend on their molecular weights. Wide angle X-ray diffraction measurements (WAXD) and DSC measurements showed that the crystals of the high molecular weight PCLs were more perfect than those of the low molecular weight ones. These results demonstrate that the concentration of the end groups of PCL chains is the main factor that influences the melting behavior. The fusion enthalpy per repeating unit (△Hu) was determined to be 11.3 kJ/mol for PCL.