Hydroformylation has been applied in the chemical industry for decades to produce n-aldehydes from 1-olefins and syngas (a mixture of CO and H2). However, the difficulty of catalyst separation and harsh operating con-ditions of conventional homogeneous hydroformylation reactions have prompted researchers to explore het-erogeneous catalytic strategies. In this work, a novel core-shell structured catalyst comprised of Rhodium nanoparticles (Rh NPs) homogeneously encapsulated in a silicalite-1 zeolite (Rh@S-1) is designed to realize a high activity in 1-hexene hydroformylation. The conversion of 1-hexene over the Rh@S-1 catalyst exhibits as high as 85.8%, and the ratio of n-heptanal to iso-heptanal reaches up to 2.5 at 90 degrees C. Multiple studies demon-strate that the outstanding catalytic activity over this core-shell structured catalyst can be explained by the highly active homogeneously dispersed Rh NPs and the distinguishable mass transfer effect of the unique and orderly micropores structure of silicalite-1 zeolite. Furthermore, by changing templating agent concentrations during the hydrothermal method, the size of the zeolite crystals can be easily controlled and is proven to be an essential factor affecting the hydroformylation performance.