Lipid membrane fusion is a fundamental process in nature. In the fusion process two distinct bilayers merge the hydrophobic layers, and an interconnected structure is produced. In this research, the fusion of polymer membrane self-assembled by cleaved pinned micelles is investigated. Disulfide-tethered poly(tert-butyl acrylate-block-styrene) diblock copolymer brushes on the surfaces of silica particles were prepared by the grafting to or grafting from method. In acetone, the diblock copolymer brushes self-assemble into pinned micelles. Upon cleavage from the surfaces of the silica particles with n-tributylphosphine, the pinned micelles self-assemble into vesicles. In the meanwhile, thiol groups at the ends of the block copolymer brushes were produced in the cleavage reaction. Because of the oxidation of the thiol groups and the formation of the disulfide bonds, the vesicle structures are fused into bigger hollow structures and fiber-like structures. The further fusion of the fiber-like structures results in precipitation of the polymer from the solution.