The current work introduces highly dispersed Pt and PtSn catalysts supported on La₂O₂CO₃ nanorods prepared via ultrasonic impregnation, which are used as probe catalysts for the liquid-phase crotonaldehyde hydrogenation. The physicochemical properties of the catalysts are assessed by means of various techniques, including XRD, TEM, XPS, H₂-TPD, in situ CO-DRIFT and X-ray adsorption fine structure (XAS). A close combination of catalyst surface experiments and the reactive performances reveals that the distinct reactive performance of the Pt and PtSn catalysts is tentatively attributed to the composition-dependent architecture of Pt–lanthanum interfaces and bimetallic particles while excluding the particle size effect. Catalytic activity tests demonstrate that incorporation of Sn into Pt catalyst brings great significance to the selective hydrogenation of carbonyl groups as it results into the structure evolution of bimetallic particles. An optimization of Sn loading and reaction conditions achieves a 5-fold and 7-fold improvement in the selectivity and yield to crotyl alcohol over the parent Pt catalyst. Lastly, it is found from the catalyst reusability study that metal particles of PtSn catalysts suffers easily from particle migration and growth compared to the Pt catalyst, most likely resulting from a weaker metal–support interaction.