Preparation of large vesicles with high stability is generally difficult. Here, we report the millimeter-scale multilayered vesicle-like hydrogel-bilayer composites with long-term stability through stabilization of the vesicular structure by polymerization of the lipid molecules and gelation of the inner solution. The well-oriented multilayered structure was examined by various methods. Reflecting the multilayered structure, the resulting vesicle-like composites exhibited extremely slow drug release behavior.