Values of the equilibrium constant and of the enthalpy of hydrogen bond complex formation (DELTAH(f)) between cholesterol and some nitrogen bases (1-butylamine, di-1-butylamine, tri-1-butylamine, triethylamine, pyridine, acetonitrile, and benzonitrile) have been determined by calorimetry and IR spectroscopy. The enthalpies found for nitriles satisfy the linear correlation of DELTAH(f) and Gutmann’s donor number, determined previously for oxygen bases. Values of DELTAH(f) for amines do not satisfy this relationship. The effect of steric hindrance in the amines on the thermodynamic data of the cholesterol-amine complex formation is discussed.