To prepare amphiphilic diblock copolymers (M100Pm), a controlled radical polymerization approach was employed, incorporating hydrophilic poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC) with hydrophobic poly(3-methoxypropyl acrylate) (PMPA). The synthesized diblock copolymers feature a PMPC block with a degree of polymerization (DP) of 100 and a PMPA block with DP (=m) values of 171 and 552. The hydrophilic PMPC block exhibits biocompatibility, such as inhibition of platelet and protein adsorption, because of its hydrophilic pendant zwitterionic phosphorylcholine groups that have the same chemical structure as cell membrane surfaces. The PMPA block exhibits hydrophilicity because of its hydrophilic ether groups; however, it is predominantly hydrophobic. In addition, PMPA exhibits biocompatibility. Because both blocks of M100Pm are biocompatible, M100Pm has potential applications in the biomedical field as an innovative material. Because of the hydrophobicity of the PMPA blocks, which were surrounded by hydrophilic PMPC shells, M100Pm aggregated when dispersed in water. M100P171 and M100P552 formed spherical micelles and vesicles, respectively. As the DP of the PMPA block increased, the aggregate size and number also increased. Doxorubicin was successfully encapsulated within the M100Pm aggregates. Given their biocompatible properties, M100Pm aggregates have potential applications in drug delivery systems.