The binding dynamics of the guests acenaphthene, phenanthrene, fluorene, and acenaphthenol with sodium cholate aggregates were studied using laser flash photolysis and fluorescence. The location of the guests in the bile salt aggregate is determined by the guest's hydrophobicity, where acenaphthene, phenanthrene, and fluorene bind to the primary aggregates, while acenaphthenol binds to the secondary bile salt aggregates. The residence time of the guests in the primary aggregates and the access of ionic species from the aqueous phase to the guest in the aggregate depend on the size and the shape of the guest. These results show that bile salt aggregates are adaptable supramolecular host systems.