Fluorophore-appended resorcinarene-based cavitands having pyrene (2) and anthracene (3) moieties attached to the rims were prepared by short synthetic routes. Both undergo reversible temperature- and acid- (CF3COOD) induced vase → kite switching as evidenced by 1H NMR spectroscopy. The 1H NMR spectra also suggest that suitably sized solvents, such as [D8]toluene, efficiently solvate the cavity, reducing the conformational flexibility. In [D12]mesitylene, both cavitands undergo remarkably stable host-guest inclusion complexation with cycloalkanes. The larger cavity of 3 preferentially hosts cyclohexane, whereas the smaller cavity of 2 forms the most stable complex with cyclopentane. The propensity for the cavitands to facilitate π–π stacking between the chromophores was confirmed by both 1H NMR and fluorescence spectroscopy. The interchromophoric interaction is strongly solvent-dependent: π–π stacking between the pyrene moieties of 2 is not as efficient in [D8]toluene, as it solvates the inner cavity and prevents the two chromophores from approaching each other. Fluorescence studies revealed an unexpectedly large conformational flexibility of the cavitand structures both in the vase and kite forms, which was further confirmed by molecular dynamics simulations. Excimer formation is most preferred in [D12]mesitylene when the cavities are empty, whereas efficient solvation or guest binding in the interior spaces reduces the propensity for excimer formation. The observed high conformational flexibility of the cavitands in solution explains previous differences from the behavior of related systems in the solid state. This study shows that the rigid, perfect vase and kite geometries found for bridged resorcinarene cavitands in the solid state are largely a result of crystal packing effects and that the conformational flexibility of the structures in solution is rather high.