Several structured catalytic reactors for the direct synthesis of the DME reaction are compared with regard to catalyst hold-up, thermal conductivity, and volumetric productivity. Adherent and homogeneous catalyst layers were obtained by washcoating independent of the substrates’ shape and alloy. Moreover, the substrate nature (FeCrAl, brass, or aluminum) and shape (parallel cell monoliths and open foams) do not modify in great extent the CO conversion values and selectivity to the different compounds. This is reasonable since the catalytic phases are the same in all cases and the existence of mass and heat-transfer limitations was negligible in the experimental conditions studied. Structuring by washcoating exhibits less catalyst inventory per reactor volume than a packed-bed monolith. However, completely packing a monolith with powder catalyst produced a decrease in the CO conversion of around 25% with respect to the coated monolith. Moreover, by means of using the obtained highest catalyst hold-up by washcoating (0.33 gcat/cm3) in a brass monolith and by increasing the reaction temperature, the temperature profiles are only slightly affected. This allows to work in an almost isothermal reactor with a volumetric productivity up to 0.20 LDME/h·cm3 at 573 K.