Traditional Rh-Fe catalysts usually exhibit high alkane or methanol selectivity due to the existence of mono iron and rhodium in the catalysts, and thus the selectivity to higher alcohols is low. To overcome this problem, in this work, YRh0.5Fe0.5O3 with perovskite structure was loaded on ZrO2 by using the citrate complexing method and used for higher alcohols synthesis. Compared with RhOx/ZrO2, YRhO3/ZrO2 and Rh-FeOx/ZrO2, the prepared YRh0.5Fe0.5YRh0.5Fe0.5O3 exhibited better activity and higher selectivity to higher alcohols, the mass fraction of higher alcohols in the total alcohols is more than 80%, especially ethanol occupied 74%. The high selectivity and activity of YRh0.5Fe0.5O3 are attributed to the formation of the homogeneous and highly dispersed Rh-Fe alloys. YRh0.5Fe0.5O3 also showed very good stability. More importantly, this preparation scheme can be extended for the preparation of other multi-component nano alloy catalysts.