NH4F etching is used as an unbiased chemical etching technique to hierarchize commercially available nano-sized ZSM-5 crystals. A structure-function relationship is reported, describing how the introduction of mesoporosity in a microporous ZSM-5 zeolite significantly increases its catalytic performance in (aqueous) n-butanol dehydration. Three parent samples are etched under two severity modes: mild (5 minutes of etching) and harsh (40 minutes of etching). Intrinsic features of the parent ZSM-5’s, such as their silanol populations, influence the outcome of the etching procedure. For all materials, crystallinity is unaffected, total pore volume increases while micropore volume is almost constant, and active site accessibility increases. For all materials, etching increases the catalytic activity for n-butanol dehydration. Cofeeding water to n-butanol further increases the stability of all catalysts. Microkinetic modeling reveals that the increased activity is related to a decreased stability of dibutyl ether (DBE), the most abundant surface intermediate. A decreased DBE adsorption energy, due to the increased accessibility of the acid sites, facilitates its desorption. NH4F etching, a flexible and easy technique to engineer zeolites' textural properties, does not affect the intrinsic nature and quantity of their active sites, leading to superior catalytic performances. Our results highlight the possibility to further increase the efficiency of zeolite catalysis in biomass conversion processes.