The complex formation between certain amino alcohols and amino acids and the crown ether (18-crown-6) and the cryptand (222) in methanol was studied by calorimetric titrations. In the case of the amino alcohols, no influence of the number of methylene groups upon the complex formation with both ligands is observed. After protonation of one amino alcohol, the value of the reaction enthalpy with 18-crown-6 is doubled. In comparison with amino alcohols, amino acids form more stable complexes with both ligands. However, favorable enthalpic changes during the complex formation are compensated for by unfavorable entropic contributions. The amino groups of the amino acids are already protonated. Even in methanol as solvent, the amino acids examined exist in their zwitterionic form.