The supramolecular host molecule heptakis-[6-deoxy-6-(2-aminoethylsulfanyl)]-β-cyclodextrin provides strong control over protein self-assembly in synthetic supramolecular protein constructs. Mono-functionalization of this modified β-cyclodextrin with a cysteine residue allows for site-selective synthetic conjugation to a protein and formation of a highly stable synthetic protein complex with a lithocholic acid conjugated protein as the interaction partner.