Several novel anilines bearing 1-adamantyl substituents that are useful for drug modification were synthesised from the corresponding 1-adamantyl (nitrophenyl) ketones. The host–guest systems of these prepared ligands with β-cyclodextrin (β-CD) were studied using electrospray ionisation mass spectrometry, NMR spectroscopy, titration calorimetry and semi-empirical calculations. The complexes with 1:1 stoichiometry were found to predominantly exist as pseudorotaxane-like threaded structures with the adamantane cage sitting deep in the cavity of β-CD close to the wider rim. Such geometry was observed for all examined amines and is independent of their structure and/or presence of protic substituents.