In this study, fibrous nanosilica (KCC-1) was functionalized with octakis[3-(3-aminopropyltriethoxysilane)propyl]octasilsesquioxane (APTPOSS) groups acting as the strong performers so that the palladium nanoparticles (Pd NPs) were well-dispersed on the fibers of the KCC-1 microspheres. The synthesized Pd/APTPOSS@KCC-1 nanocatalyst exhibited excellent catalytic activity for one-pot new C–H activation.