Formation of the charge-transfer complexes between various calix[4]crowns (1-4) and [60]fullerene were studied in toluene solution using UV-vis spectrophotometry. The stability constants and the thermodynamic data of the resulting 1:1 complexes were determined and were found to decrease with increasing the size of the crown moiety of the calixcrown. Except the complex of 3, all the complexes were found to be enthalpy stabilized but disfavored in terms of entropy.