AbstractThe 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) MnGaO_x‐Spinel gives 40 % CO conversion, 81 % light olefins selectivity, and a 0.17 g g_cat⁻¹ h⁻¹ space‐time yield of light olefins in combination with SAPO‐18. In comparison, solid solution MnGaO_x (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 MnGaO_x‐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.