A supramolecular toolbox approach for multivalent ligand–receptor recognition was established based on β-cyclodextrin vesicles (CDVs). A series of bifunctional ligands for CDVs was synthesised. These ligands comprise on one side adamantane, enabling the functionalisation of CDVs with these ligands, and either mannose or sulphate group moieties on the other side for biological receptor recognition. The physicochemical properties of the host–guest complexes formed by β-cyclodextrin (β-CD) and adamantane were determined by isothermal titration calorimetry (ITC). Ligand–lectin interactions were investigated by surface plasmon resonance experiments (SPR) for the mannose ligands and the lectin Concanavalin A (ConA). Microscale thermophoresis (MST) measurements were applied for sulphate-dependent binding to L-selectin. In both cases, a multivalent affinity enhancement became apparent when the ligands were presented on the CDV scaffold. Furthermore, not only the clustering between our supramolecular mannosylated complex and Escherichia coli (E. coli), expressing the lectin FimH, was visualised by cryo-TEM, but also the competitive character to detach bound E. coli from a cell line, representing the uroepithelial cell surface, was demonstrated. In summary, a facile and effective supramolecular toolbox was established for various ligand–receptor recognition applications.