A series of MOPEO-b-PCL diblock copolymers (DBCs) with MnMOPEO=2.5 center dot 103 and MnPCL=(0.28 divided by 2.43)center dot 104 was synthesized using the anionic ring-opening block copolymerization. A bulk structure of the copolymers was studied with DSC. One glass transition and three melting peaks for MOPEO-b-PCL were found, thus implying the existence of separate crystalline domains of both blocks in a copolymer structure. The intense micellization of DBCs in dioxane/aqueous solutions was found with a spectrophotometry, a static light scattering, and photography. A reduction in CMC and an increase in -G degrees values with growth of the PCL length and at the addition of prednisolon (PS) were established. The hydrogen bonding of PS with DBCs was confirmed with FTIR spectroscopy.