Pt-Co bimetallic catalysts were deposited on γ-Al2O3 nanoparticles by atomic layer deposition (ALD) and were used for selective hydrogenation of cinnamaldehyde (CAL) to cinnamyl alcohol (COL). High resolution transmission electron microscopy, hydrogen temperature-programmed reduction, X-ray diffraction, and X-ray photoelectron spectroscopy were used to identify the strong interaction between Pt and Co. The obtained catalysts with an optimal Pt/Co ratio achieved a COL selectivity of 81.2% with a CAL conversion of 95.2% under mild conditions (i.e., 10 bar H2 and 80 °C). During the CAL hydrogenation, the addition of Co on Pt significantly improved the activity and selectivity due to the synergetic effects of Pt-Co bimetallic catalysts, resulted from the transfer of electrons from Co to Pt, which can stabilize the carbonyl groups. The obtained Pt-Co bimetallic catalysts also showed excellent stability due to the strong interaction between the metal nanoparticles and the alumina support. Negligible losses in the activity and selectivity were observed during the recycling experiments, showing the potential for practical applications.