Hydrophobic guests such as pyrene could be readily trapped inside the micelles of an alkynylated surfactant in the presence of an azide-functionalized cross-linker using the click reaction. The cross-linker was designed to contain cleavable bonds such as geminal diol, disulfide, and acetal. The resulting pyrene-containing water-soluble nanoparticle was under electrostatic stress when diluted below the CMC of the surfactant. Extremely rapid (<1 min) release of the hydrophobic content was observed when the cross-linker was cleaved. This method combines the ease of physical entrapment and the precision of chemical ligation, and potentially is highly useful in the delivery and controlled release of pharmaceutical agents.