The aim of this study was to evaluate the efficiency of catalytic ozonation to increase the degradation of aqueous N-methyldiethanolamine (MDEA) solutions, using two lamellar double hydroxides, namely MgxFe-LDH with x = Mg/Fe = 2, 3, were synthesized by the simple and rapid co-precipitation method. Then, the obtained materials were calcined at 400 °C for 6 h. The calcined products were respectively designated as HTcMg2Fe and HTcMg3Fe, and characterized by powder X-ray diffraction (XRD), N2 physisorption (BET), Fourier transform infrared spectra (FT-IR), and scanning electron microscopy (SEM). The powders produced were used in the ozonation reaction to remove MDEA from aqueous solutions. Experimental results showed that the highest MDEA removal efficiency is in the catalytic ozonation process. Under the optimal conditions for heterogeneous catalytic ozonation of MDEA: initial concentration of 4 Wt% MDEA, 30 °C, catalyst mass of 30 mg/100 ml solution, and contact time of 60 min. The results showed the highest percentage of COD removal, which was up to 80.76% for HTcMg2Fe higher than that of HTcMg3Fe 80.36%.