A series of ZSM-35 zeolites with different alkaline treatment degrees were prepared. The precise effects of alkaline treatment on composition, morphology, porosity, transportation and acidity of the samples were characterized by means of multiple techniques including N2 sorption, transmission electron microscopy (TEM), intelligent gravimetric analyzer (IGA) and Fourier transform infrared spectroscopy (FTIR). ZSM-35 after moderate alkaline treatment exhibited enhanced carbonylation activity compared with the parent sample. As revealed by the N2 adsorption and TEM results, alkaline treatment could induce the deaggregation of ZSM-35 clusters and remove the amorphous debris on the surface of ZSM-35 platelets. Furthermore, an improved diffusion behavior of the dimethyl ether reactant molecule was observed on the alkali-treated sample from IGA experiments which directly led to the better catalytic performance for the carbonylation of the dimethyl ether with carbon monoxide. Mesoporosity created by severe alkaline leaching does not enhance the catalytic properties of ZSM-35 in dimethyl ether carbonylation reaction. Especially, a decrease in reaction stability was observed due to the limitation effect of carbonaceous deposit formation.