The PtFe catalysts supported on the La₂O₂CO₃ nanorods with various Fe loadings are constructed at the atomic level. The composition and structure of the resultant catalysts are analyzed by ICP-OES, XRD, TEM, H₂-TPR, H₂-TPD and XPS techniques. A subsequent study of crotonaldehyde hydrogenation over the catalysts shows that the iron addition exerts great influence on the catalyst structure and the associated reactive performance. The surface oxygenated groups of La₂O₂CO₃ afford a high dispersion of Pt due to the interfacial confinement effect. The Pt-support interfaces are wrecked by Fe atoms located on the catalyst surface, simultaneously producing bimetallic surfaces. Both surface studies and catalytic reaction experiment on the catalysts illustrate that an increased electronic density on Pt and the structure evolution of metal particles upon Fe addition is tentatively proposed to be accounted for the distinct catalytic behaviors. Under the working conditions, the highest selectivity toward the desired crotyl alcohol of the Fe-promoted catalysts is two-fold higher than that of the Pt/La₂O₂CO₃.