Sn-based zeolite have been prepared by incipient wetness impregnation by studying the role of the starting precursor either Sn(II) or Sn(IV) chlorides. Catalysts have been deeply characterized through XRD, FT-IR, UV–vis-NIR, SEM-EDXS, FE-SEM-EDXS, and IR of probe molecules i.e., pyridine and CO, by also investigating the reaction at the surface in static conditions. As well catalytic activity has been carried out by investigating the role of GHSV that has been varied between 2700 and 8500 h−1, obtaining linear variation of product distribution as a function of contact time. Small amounts of Sn improve the catalytic activity of H-ZSM-5 zeolite in converting ethanol to higher hydrocarbons. In particular, the addition of Sn4+ ions increases the conversion of ethanol to C6–C8 aromatic hydrocarbons up to a very interesting 34 % selectivity at 100 % ethanol conversion. In fact, bioethanol conversion over Sn–H-ZSM-5 zeolite represents a potentially interesting way to produce a high-octane biogasoline, as well as aromatic (BTX) cut useful as a renewable intermediate in future biorefinery-derived processes. It is proposed that ethylene, the main product, is the key intermediate in the acid-catalyzed route, and Sn-ions are favoring the cyclization and dehydrogenation of ethylene-derived oligomers.