AbstractThe selective hydrogenation of α,β‐unsaturated aldehydes to unsaturated alcohols is an important process for many industrial applications, whereas the realization of excellent conversion efficiency and selectivity remains a significant challenge. Herein, we report the preparation of a class of networked Pt–Sn nanowires (Pt–Sn NWs) for the selective hydrogenation of unsaturated aldehydes to the desired unsaturated alcohols. The optimized Pt1.5Sn NWs delivered a high conversion efficiency (98.1 %) for the hydrogenation of cinnamaldehyde (CAL) and excellent selectivity to cinnamyl alcohol (COL) (90.6 %); thus, they outperformed Pt1.5Sn nanoparticles (NPs) as well as Pt NPs. The high performance of the Pt1.5Sn NWs was expanded to the hydrogenation of other α,β‐unsaturated aldehydes. X‐ray photoelectron spectroscopy revealed that a high ratio of metallic Pt in the Pt1.5Sn NWs boosted the conversion of CAL and that a high Sn content favored the hydrogenation of the C=O bond, both of which lead to excellent activity and selectivity.