Chemical etching with fluoride ions is a new approach for secondary porosity engineering of aluminosilicate zeolite frameworks. This work shows that the mixture of HF and NH4F extracted indiscriminately both framework Si and Al from ZSM-5 zeolite. After the treatment, the relative crystallinity decreased slightly; the external surface areas and mesopore volumes increased, but the micropore surface areas and volumes and the acidity of the obtained hierarchical ZSM-5 did not change appreciably. When the hierarchical materials were applied in the reaction of methanol to gasoline (MTG), the catalyst lifetime was prolonged significantly with the liquid hydrocarbon selectivity improved slightly. The results can be ascribed to the improved transport through the crystals coupled with the retained zeolite acidity.