Monolayers of octadecane-2,4-dione on the surfaces of EuCl3 and TbCl3 solutions in the concentration range of 1 × 10–4 to 5 × 10–3 M at pH 5.8 are studied. It is found that the limiting area of octadecane-2,4-dione molecule in a monolayer dependence on Eu3+ and Tb3+ concentration is of extreme nature. The formation of complex compounds in the ligand monolayer is postulated, and structures are proposed for these compounds at different concentrations of metal ions.