Abstract: Dual active sites from acidic zeolite and Pd are not only capable of catalyzing multiple type of reactions, but could also generate unique functions owing to the synergy between metals and acidic sites. However, there are only a few reports on the investigation of the synergy of acid/Pd dual sites in TS-1. Herein, TS-1 confined Pd catalyst with mesoporous silica shell (Pd@TS-1 @meso-SiO2) has been successfully synthesized and its synergy effect contributes to the enhanced conversion rate (19.2%) and selectivity (74.7%) on styrene oxidation. The interaction between Pd and TS-1 has been investigated by EPR and 1H NMR techniques, the experimental measurements show an obvious change in the signal distribution of weakly acidic terminal hydroxyls and hydrogen-bonding silanols. The schematic illustration of selective styrene oxidation in the model of Pd@TS-1 @meso-SiO2 is proposed to clarify the synergistic effect on styrene oxidation between TS-1 and Pd nanoparticles at an atomic-/nanoscale.