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 N2 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.