Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper (Cu/HMOR) catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.