In this paper, natural kaolinite was chemically, thermally, mechanically and mechano-chemically treated and, characterized through XRD, FTIR, HRTEM, SEM, NH3-TPD and TGA techniques. The catalytic activity of different modified kaolinite samples was investigated in the preparation of DME by methanol dehydration, seriously lacking in the literature as a cheap source for DME. The textural and structural changes in all samples were correlated with conversion% of methanol and selectivity to DME.