The selective hydrogenation of cinnamaldehyde (CAL) to prepare cinnamyl alcohol (COL) is challenging as the unwanted hydrogenation of CC bond in CAL is thermodynamically more favorable than the hydrogenation of CO bond. We herein designed core–shell structured nanoparticles (NPs) that consisted of Pt cores and Sn shells to catalyze the CAL to COL conversion. By simply changing the amount of Sn precursor, we generated Pt@Sn NPs with different Sn shell thickness and catalytic performance. Among the samples, Pt@Sn/SiO2 with Pt/Sn of 1/1 achieved the highest CAL conversion (87.2 %) as well as the COL selectivity (95.4 %), which were 5-fold and 6-fold, respectively, higher than those of Pt/SiO2. This catalyst was also applicable to the hydrogenation of other α, β-unsaturated aldehyde and unsaturated carbonyl compounds. Both experiments and theoretical calculations indicated that the strong Pt-Sn interaction and the partial coverage of Pt by Sn facilitated their adsorption of CO bonds, thus enhancing the conversion of CAL and the selectivity towards COL.