Hydrothermal synthesis of ZSM-35 using dioxane as the structure-directing agent resulted in more than half of Al atoms located at the T4 site in the 8 membered-ring pore. The Brønsted acid site, thus generated, efficiently catalyzed the carbonylation of dimethyl ether with a specific activity of 1.2 mol_MA mol_T4⁻¹ h⁻¹ at 493 K.