Pillar[n]arene-based supramolecular polymers have attracted great interest because of their tunable morphologies and external stimuli responsiveness. However, most of the investigations of supramolecular polymers previously reported were focused on their formation and transformation, and investigations on their applications are rare. Herein, we designed and prepared hybrid polymeric materials by incorporating Pd nanoparticles into a supramolecular polymer, constructed from a pillar[5]arene dimer and a three-arm guest. The obtained hybrid polymer was fully characterized by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy-energy-dispersive X-ray mapping, and X-ray diffraction technologies. Importantly, the hybrid supramolecular polymeric materials exhibited desirable catalytic activity for reductions of toxic nitroaromatics and C-C bond-forming Suzuki-Miyaura reaction in aqueous solution.