Novel fibrous nano-silica (KCC-1) was functionalized with chlorodiphenylphosphine with phosphine-functionalized nanoparticle groups acting as strong performers, so that gold(III) could form complexes without aggregation on the fibers of KCC-1/PPh₂ microspheres (KCC-1/PPh₂/Au). Compared to the traditional mesoporous silica materials, KCC-1 remarkably enhances the accessibility of gold(III) due to its three dimensional hierarchical channel structure. HPG@KCC-1/PPh₂/Au NPs were used for the first time as a catalyst for the C–C cross-coupling between allylarenes or methyl acrylate and benzoxazole, and they showed excellent catalytic activities under green conditions.