Zeolite-catalyzed carbonylation of dimethyl ether to methyl acetate represents a new route to synthesize acetyls. A rod-shaped HSUZ-4 zeolite, with intersecting 10-member ring and 8-member ring channels, showed exceptionally high activity and durability, as compared to the HZSM-35 sharing a similar pore structure. The abundant openings of 8-member ring pores, as determined by the shape of HSUZ-4, facilitated the diffusion of the reactive molecules.