Selective hydrogenation of benzaldehyde is a green and sustainable technology to produce benzyl alcohol. Herein, we report a hybrid nano-structure catalyst(Pd/@-ZrO2/AC) by photochemical route for selective hydrogenation of benzaldehyde under mild reaction conditions. The Pd/@-ZrO2/AC catalyst exhibited outstanding activity(100%) and high selectivity for benzyl alcohol (> 98 %), much higher than that of Pd/ZrO2 and Pd/AC. The high catalytic activity was attributed to the special structure and the synergistic effect. A series of Pd/@ -MexOy/AC(MexOy: TiO2, CeO2, La2O3) catalysts further confirmed the synergistic effect in this hybrid nanostructure for this reaction. This work clearly demonstrates that loading nano-metal on high specific surface area materials with nano-semiconductors can increase the catalytic activity and open up a new direction for the synergistic catalysis of hybrid nano-structure catalysts.