A new heterodimeric crown amphiphile was fabricated, wherein the oxacrown and selencrown ethers provided the desired molecular framework for hydrophilicity and hydrophobicity, respectively. From an integrated perspective, the developed amphiphile possesses features of crown ethers, amines, and selenium-containing species, and its assembly in water can be responsive to diverse chemical effectors-H2O2 and CO2 in a switchable ON/OFF mode to achieve controlled release. It is the first case wherein the applications of cyclic polyethers with different solubilities drives the self-assembly in an aqueous medium.