The potential of hierarchical H‐ZSM‐5 zeolites was studied for the conversion of DME to fuel‐compatible hydrocarbons. For this purpose, hierarchical H‐ZSM‐5 zeolites have been prepared from commercial H‐ZSM‐5 by desilication and organosilane‐directed hydrothermal synthesis. The zeolites were characterized by X‐ray diffraction, NH3‐TPD, DRIFTS, and N2 physisorption measurements. The catalysts have been tested in a tube reactor (1 bar, 648 K). The results indicate important structural changes in framework and acidic sites, which are significant for the synthesis of gasoline‐range hydrocarbons.