The conversion of syngas to higher oxygenates is an important step in the pathway towards the long-term sustainable production of fuels and chemicals. Mixed Cu/Fe catalysts combine metals with different CO activation characteristics, a property that makes them promising candidates for higher oxygenate production. However, Cu/Fe catalysts suffer from instability due to sintering and phase separation, and the active sites for higher oxygenate formation on these materials are not well understood. In this work, we use atomic layer deposition (ALD) to modify silica-supported Cu nanoparticles with monolayer precise amounts of Fe2O3 and study the effects on catalyst structure, reactivity, and stability. We demonstrate that the Fe2O3 ALD process is inherently selective towards deposition on the SiO2 surface versus the Cu nanoparticles. As a result, a sufficiently thick Fe2O3 layer surrounding the Cu nanoparticles acts as a barrier against Cu migration, preventing catalyst deactivation through sintering without covering the Cu. In syngas conversion reactions, we find that higher oxygenate selectivity increases with Fe2O3 loading at low and intermediate ALD cycle numbers. Furthermore, using in situ X-ray absorption spectroscopy, we demonstrate that the Fe near the Cu nanoparticles is reduced to a metallic state under reaction conditions. From these measurements, we identify these metallic Cu/Fe interfaces as the active sites for higher oxygenate formation, which are most abundant at intermediate Fe2O3 ALD cycle numbers. As the Fe2O3 loading increases, higher oxygenate selectivity falls, resulting from encapsulation of the Cu nanoparticles by thick Fe2O3 layers. The results demonstrate how thickness-controlled ALD Fe2O3 can be used as both a promoter and stabilizer of Cu-based higher oxygenate synthesis catalysts.