We report the synthesis and X-ray crystal structures of three acyclic CB[n]-type molecular containers (, , ) that differ in the charge on their solubilizing groups (SO3(-), OH, NH3(+)). The X-ray crystal structures of compounds and reveal a self-folding of the ArOCH2CH2X wall into the cavity driven by π-π interactions, H-bonds and ion-dipole interactions. The need to reverse this self-folding phenomenon upon guest binding decreases the affinity of and toward cationic guests in water relative to as revealed by direct (1)H NMR and UV/Vis titrations as well as UV/Vis competition experiments. We determined the pKa of 6-aminocoumarin (pKa = 3.6) on its own and in the presence anionic, neutral, and cationic hosts (: pKa = 4.9; : pKa = 4.1; , pKa = 3.4) which reflect in part the relevance of direct ion-ion interactions between the arms of the host and the guest toward the recognition properties of acyclic CB[n]-type containers. Finally, we showed that the weaker binding affinities measured for neutral and positively charged hosts and compared to anionic results in a decreased ability to act as solubilizing agents for either cationic (tamoxifen), neutral (17α-ethynylestradiol), or anionic (indomethacin) drugs in water. The results establish that acyclic CB[n] compounds that bear anionic solubilizing groups are most suitable for development as general purpose solubilizing excipients for insoluble pharmaceutical agents.