A combination of reactivity and structural studies using X-ray diffraction (XRD), pair distribution function (PDF), and transmission electron microscopy (TEM) was used to identify the active phases of Fe-modified Rh/TiO2 catalysts for the synthesis of ethanol and other C2+ oxygenates from CO hydrogenation. XRD and TEM confirm the existence of Fe-Rh alloys for catalyst with 1-7 wt% Fe and similar to 2 wt% Rh. Rietveld refinements show that FeRh alloy content increases with Fe loading up to similar to 4 wt%, beyond which segregation to metallic Fe becomes favored over alloy formation. Catalysts that contain Fe metal after reduction exhibit some carburization as evidenced by the formation of small amounts of Fe3C during CO hydrogenation. Analysis of the total Fe content of the catalysts also suggests the presence of FeOx also increased under reaction conditions. Reactivity studies show that enhancement of ethanol selectivity with Fe loading is accompanied by a significant drop in CO conversion. Comparison of the XRD phase analyses with selectivity suggests that higher ethanol selectivity is correlated with the presence of Fe-Rh alloy phases. Overall, the interface between Fe and Rh serves to enhance the selectivity of ethanol, but suppresses the activity of the catalyst which is attributed to the blocking or modifying of Rh active sites. (C) 2015 Elsevier Inc. All rights reserved.