Surfactant complexes of octanoyl alanine [CH3(CH2)6CONHCH(CH3)COOH] containing magnesium, calcium and zinc ions, respectively, were synthesized by the reactions of octanoyl alaninate ligand with hydroxide of magnesium, calcium or zinc under different molar ratio conditions in this study. The solubility of the complex in the pure solvent and water/organic solvent was tested. The results showed that the complexes of magnesium and calcium had a high solubility in most of the pure solvent and water/organic solvent, whereas the solubility of complex of zinc was very little in the pure solvent and water/organic solvent. Furthermore，the aggregation behavior of the above surfactant complexes in the pure solvent and water/organic solvent were analyzed by nuclear magnetic resonance (NMR) spectrometry, electrical conductivity, vapor pressure depression (VPO) and FT-IR. The results showed that the complexes of Mg(oct-ala)2, Ca(oct-ala)2 and Zn(oct-ala)2 were easy to aggregate and form Reverse micelle in the pure solvent and water/organic solvent, which is due to adsorbing water.