Bile salt aggregates are supramolecular structures with two types of binding sites, called primary and secondary sites. The objective of this work was to explore how the nonplanarity and size of guests (biphenyl [BP], 1-1′-binaphthyl [BNP] and dibenz[b,f]oxepin [DBX]) affected their binding affinity and dynamics to sodium cholate (NaC) aggregates. Fluorescence and laser-flash photolysis experiments were performed to obtain information on the binding environment for the guests, the accessibility of quenchers to guests in the aggregate and the dissociation rate constants of the guests from the aggregates. All guests were bound to the more hydrophobic primary aggregate, showing that this site can accommodate nonplanar molecules. However, the structure of the guest affects the structure of the primary aggregates, leading to changes in the accessibility of anions to aggregate-bound guests and to changes for the guest dissociation rate constants from the aggregates.