Breaking the trade-off between activity and selectivity has been a long-standing challenge in the field of catalysis. We demonstrate the importance of disentangling the target reaction from the secondary reactions for the case of direct syngas conversion to light olefins by incorporating germanium-substituted AlPO-18 within the framework of the metal oxide–zeolite (OXZEO) catalyst concept. The attenuated strength of the catalytically active Brønsted acid sites allows enhancing the targeted carbon-carbon coupling of ketene intermediates to form olefins by increasing the active site density while inhibiting secondary reactions that consume the olefins. Thus, a light-olefins selectivity of 83% among hydrocarbons and carbon monoxide conversion of 85% were obtained simultaneously, leading to an unprecedented light-olefins yield of 48% versus current reported light-olefins yields of ≤27%.

The oxide–zeolite (OXZEO) catalyst design concept has been demonstrated in an increasing number of studies as an alternative avenue for direct syngas conversion to light olefins. We report that face‐centered cubic (FCC) MnGaOx‐Spinel gives 40 % CO conversion, 81 % light olefins selectivity, and a 0.17 g gcat−1 h−1 space‐time yield of light olefins in combination with SAPO‐18. In comparison, solid solution MnGaOx (characterized by Mn‐doped hexagonal close‐packed (HCP) Ga2O3) with a similar chemical composition gives a much inferior activity, i.e., the specific surface activity is one order of magnitude lower than the spinel oxide. Photoluminescence (PL), in situ Fourier‐transform infrared (FT‐IR), and density functional theory (DFT) calculations indicate that the superior activity of MnGaOx‐Spinel can be attributed to its higher reducibility (higher concentration of oxygen vacancies) and the presence of coordinatively unsaturated Ga3+ sites, which facilitates the dissociation of the C−O bond via a more efficient ketene–acetate pathway to light olefins.