Dimethyl ether (DME) synthesis from syngas over a mixture of a methanol synthesis catalyst (ZnO, 25.10 wt %; AuO, 64.86 wt %; Al 2 O 3 , 10.04 wt %) and a methanol dehydration catalyst (γ-A1 2 O 3 ) has been investigated for one-, two-, and three-layer catalyst beds. There is a common regularity for these three variants: with an increasing temperature, the total CO conversion decreases, the CO-to-methanol conversion decreases, and the CO-to-DME conversion increases. The largest values of DME selectivity and DME yield have been attained with the three-layer bed. The highest DME yield has been obtained at 250–285°C. Use of a mechanical mixture of the methanol synthesis catalyst and alumina makes it possible to efficiently obtain DME from syngas ballasted with nitrogen (20 vol %) at an H 2 /CO ratio of 1, which is unfavorable for methanol synthesis. The DME yield on the syngas input basis in this case with the ballast gas (nitrogen or CO 2 ) taken into account can be about 10 wt %.