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Allylic alcohols typically produced through selective hydrogenation of <i>α</i>,<i>β</i>-unsaturated aldehydes are important intermediates in fine chemical industry, but it is still a challenge to achieve its high selectivity transformation. Herein, we report a series of TiO₂-supported CoRe bimetallic catalysts for the selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL) using formic acid (FA) as a hydrogen donor. The resultant catalyst with the optimized Co/Re ratio of 1:1 can achieve an exceptional COL selectivity of 89% with a CAL conversion of 99% under mild conditions of 140 °C for 4 h, and the catalyst can be reused four times without loss of activity. Meanwhile, the Co₁Re₁/TiO₂/FA system was efficient for the selective hydrogenation of various <i>α</i>,<i>β</i>-unsaturated aldehydes to the corresponding <i>α</i>,<i>β</i>-unsaturated alcohols. The presence of ReO_x on the Co₁Re₁/TiO₂ catalyst surface was advantageous to the adsorption of C=O, and the ultrafine Co nanoparticles provided abundant hydrogenation active sites for the selective hydrogenation. Moreover, FA as a hydrogen donor improved the selectivity to <i>α</i>,<i>β</i>-unsaturated alcohols.