Here we developed a novel CO2-responsive pillararene-based molecular recognition motif established from a water-soluble pillar[5]arene and an anionic surfactant, sodium dodecyl sulfonate (SDS). The inclusion complex acted as a supramolecular amphiphile and self-assembled into spherical bilayer vesicles as confirmed by DLS, SEM, and TEM experiments. These vesicles were disrupted upon bubbling N-2 or adding much more SDS to eliminate the inclusion complex. The assembly and disassembly of vesicles were successfully employed in gas and surfactant triggered releases of calcein, a water-soluble dye.