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Abstract In this work, the production of dimethyl ether (DME) from methanol over natural kaolin clay modified through impregnation with various percentages of H2SO4, WO3, or ZrO2 catalysts was investigated. The prepared catalysts were characterized via X-ray fluorescence, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and N2-sorption analysis. The acidity of these catalysts was determined through the dehydration of isopropyl alcohol and the chemisorption of pyridine. The catalytic activity performance revealed that the addition of modifiers into kaolin enhanced the latter’s activity toward DME production. In addition, the kaolin clay modified with 10 wt% ZrO2 exhibited excellent activity of 98% conversion with 100% selectivity at 275 °C. Moreover, this catalyst could proceed the reaction for a long time (6 days) without any noticeable deactivation. The remarkable improvement in the catalytic performance achievement was well correlated with the acidity and the structure of the catalysts.