The 1Н, 13С, 15N, and 111Cd NMR spectra of a series of metallated alkanol ammonium ionic liquids (MAIL) series [n N(CН2СН2ОН)3М]+ · mХ−, where М = Cd, Mg, Zn, Fe, Rh; Х = Cl, ООCСН3, obtained in a wide range of temperatures of the studied samples, have been analyzed. It is found that, under biomimetic conditions (Н2О, 25 °С), the compounds studied exist as mono- bi- and the tricyclic structures, which are in equilibrium. Shift of the equilibrium depends upon nature of a metal and effects all the parameters of the NMR spectra. Peculiarities of ligand exchange, typical for the studied compounds, have been studied in a wide range of temperatures. It is found that the NMR data can be used to control structure of the compounds formed in the course of synthesis.