Mordenite (H-MOR) catalysts were synthesized by a hydrothermal method, and silver-modified mordenite (Ag-MOR) catalysts were prepared by ion exchange with AgNO3 at different concentrations. The performance of these catalysts in the carbonylation of dimethyl ether (DME) to methyl acetate (MA) was also evaluated. The catalysts were characterized by Ar adsorption/desorption, XRD, ICP-AES, SEM, HRTEM, 27Al NMR, H2-TPR, NH3-TPD, Py-IR, and CO-TPD. According to the characterization results, Ag ion exchange sites were mainly located in the 8-membered ring (8-MR) channels of Ag-MOR; evenly dispersed Ag2O particles were also present. The acid site distribution was changed by the modification of Ag, and the amount of Brønsted acid sites increased in 8-MR and decreased in 12-MR. The CO adsorption performance of the catalyst significantly increased with the modification of Ag. These changes improved the conversion and selectivity of the carbonylation of DME. Over 4Ag-MOR in particular, DME conversion and MA selectivity reached 94% and 100%, respectively.