Palladium nanoparticles supported on carbon nanotubes (CNT) functionalized with various organosilane modifiers have been prepared through a post-synthesis grafting method followed by a metal adsorption-reduction approach. The surface property, catalyst structure, electrochemical activity, and catalytic performance were tested in the selective aerobic oxidation of benzyl alcohol. The variation in type and amount of surface-functional groups played a key role in controlling catalytic behavior through fine tuning the surface basicity, metal nanoparticle size and size distribution, metal-support electronic interaction. In all these tested organosilane modifiers, 3-aminopropyl triethoxysilane exhibited the largest improvement in catalytic performance, with a remarkably high quasi-turnover frequency of 288,755 h(-1) based on the electrochemical active surface area. (C) 2014 Elsevier B.V. All rights reserved.