Vesicles formed by ABCA tetrablock copolymers in solvents that are selective for block A are studied using the Monte Carlo simulation. Simulation results show that the chain length ratio and hydrophobicity of blocks B and C are key factors determining the hydrophobic layer structure of the vesicles. lithe B and C blocks are of the same hydrophobicity, the longer block C tends to form the closed hydrophobic layer, whereas the shorter block B is located on the outer surface of the closed hydrophobic layer. However, if the hydrophobicity difference between blocks B and C is high enough, the reverse will occur given that block B has a higher hydrophobicity and block C has a lower hydrophobicity. The kinetics of vesicle formation is also studied. Simulation results reveal that the hydrophobic layer structure is formed through the migration of the polymer chain within the vesicle membrane after the formation of the vesicle profile. This migration is independent of the differences in chain length ratio and the hydrophobicity between the blocks B and C. The packing mode and the migration of polymer chains within the vesicle membrane are also presented and discussed.