Catalytic conversion of Syngas and dimethyl ether to ethanol is a green strategy of harnessing fine chemicals from nonpetroleum origins. In the process, catalyst deactivation coupled with higher byproduct selectivities is still a serious cause of concern due to inevitable yield losses. Herein, we synthesized highly ordered Cu-MOR@SiO2 core-shell microcapsules, employing a facile scalable surfactant-directed sol-gel technique. Comparably, the microcapsules displayed higher DME carbonylation (83.8%) activity and a remarkable product yield (48.7%). Furthermore, confinement of Cu-MOR particles surrounded by SiO2 crystals cushions dispersed Cu components from inevitable sintering during exposure to higher temperatures, paving way for an effective regeneration treatment. However, this catalyst will function in tandem with commercialized CZA catalyst in a dual bed reactor. The novel Cu-MOR@SiO2 encapsulated catalyst displayed a stable longer service life and higher product yield, thus providing the dual bed ethanol synthesis pathway from cofeeding dimethyl ether and syngas, an opportunity toward commercial production.