Composites of Ga2O3 clusters and zeolite ZSM-5 were evaluated for the transformation of methanol to hydrocarbons. Comparison of the activity with ZSM-5 showed that the Ga2O3 clusters are responsible for the enhanced selectivity to aromatics via contact synergy, thus showing the importance of non framework gallium species for this reaction. TEM analysis of fresh and spent catalysts allowed the identification of the formation of carbonaceous products at the Ga2O3/zeolite interface region, and this interface is also the probable location of the catalyst active sites.