A series of amphiphilic block copolymers mPEO-b-PCL with different PCL molecular weight were successfully prepared by combination of anionic ring-opening polymerization with coordination-insertion ring-opening polymerization. Firstly, the linear mPEO was prepared by anionic ring-opening copolymerization of EO with 2-(2-methoxyethoxy) ethoxide potassium as the small molecule initiators, then the mPEO as the macroinitiator was used to initiate the ring-opening polymerization of CL, in the absence of Sn(Oct)2 as the catalyst, and amphiphilic block copolymers mPEO-b-PCL were obtained. By changing the ratio of monomer and macroinitiator, prepared a series of different molecular weight mPEO-b-PCL. The structure of intermediates and final products were characterized by 1H NMR and GPC. The critical micelle concentration (cmc) of the final copolymer was measured. In addition, the sizes and morphologies of the obtained micelles at different PCL chains were studied with Laser nano-particle size analyzer and transmission electron microscopy (TEM).