Giant vesicles with several-micrometer diameters were prepared by the self-assembly of an amphiphilic block copolymer in the presence of the Belousov-Zhabotinsky (BZ) reaction. The vesicle is composed of a non-uniform triblock copolymer synthesized by multi-step reactions in the presence of air at room temperature. The triblock copolymer contains poly(glycerol monomethacrylate) (PGMA) as the hydrophilic block copolymerized with tris(2,2'-bipyridyl)ruthenium(II) (Ru(bpy)), which catalyzes the BZ reaction, and 2-hydroxypropyl methacrylate (HPMA) as the hydrophobic block. In this new approach, the radicals generated in the BZ reaction can activate a reversible addition-fragmentation chain transfer (RAFT) polymerization to self-assemble the polymer into vesicles with diameters of approximately 3 µm. X-ray photoelectron spectroscopy (XPS) measurements demonstrated that the PGMA--Ru(bpy)--PHPMA triblock copolymer is brominated and increases the osmotic pressure inside the vesicle, leading to micrometer-sized features. The effect of solvent on the morphological transitions are also discussed briefly. This BZ strategy, offers a new perspective to prepare giant vesicles as a platform for promising applications in the areas of microencapsulation and catalyst support, due to their significant sizes and large microcavities.