Supramolecular complexation of - and fullerenes with 37-allyl-38,39,40,41,42-pentahydroxy-5,11,17,23,29,35-hexa(4-tert butyl)calixarene (I) has been studied in CCl(4) medium by NMR spectrometric method. All of the complexes are found to be stable with 1:1 stoichiometry. Formation constants (K) of the above supramolecular complexes have been determined from systematic variation of NMR chemical shifts of specific protons of I in the presence of - and fullerenes. Trends in the K value suggest that fullerene binds more strongly with I relative to fullerene. Both PM3 and ab initio calculations reveal that the intermolecular interaction in the fullerene/I complex proceeds through quite deep energy minima.