The supramolecular dynamics of triplet excited states of the 2-naphthol@dendrimer (2-NpOH@n-SBD) noncovalently bound complex have been studied by fluorescence spectroscopy and laser flash photolysis. By varying the acidity and dendrimer size, polyamidoamine dendrimers are shown to possess both nonspecific and specific binding properties. For example, the studies show that 2-naphthol binds preferentially to the tertiary amine groups within the dendrimer interior and can be released by lowering the pH of the solution. On a per binding site basis, studies of the dynamics of (3)2-NpOH*@n-SBD reveal that the overall dynamics (entry and exit rate constants) are enhanced by increasing the acidity of the solution. Furthermore, the amount of protonation of tertiary amine groups within 2-SBD, 4-SBD, and 6-SBD was determined to be similar to 12%, similar to 10%, and <1%, respectively, at pH 6. The results presented here demonstrate that, in addition to being able to complex transition metals, organic molecules that are capable of hydrogen bonding to the internal amine moieties can also be bound to dendrimers.