Much attention has been increasingly focused on the applications of noble metal nanoparticles (NPs) for the catalytic degradation of various dyes and pigments in industrial wastewater. We have demonstrated that Pd NPs/Fe3O4-PEI-RGO nanohybrids exhibit high catalytic activity and excellent durability in reductive degradation of MO, R6G, RB. Specific surface area was successfully prepared by simultaneous reduction of Pd(OAc)2 chelating to PEI grafted graphene oxide nanosheets modified with Fe3O4. The as-prepared Pd NPs/Fe3O4-PEI-RGO nanohybrids were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, high-resolution TEM and energy dispersive X-ray spectroscopy, and UV-lambda 800 spectrophotometer, respectively. The catalytic activity of Pd NPs/Fe3O4-PEI-RGO nanohybrids to the degradation of MO, R6G, RB with NaBH4 was tracked by UV-visible spectroscopy. It was clearly demonstrated that Pd NPs/Fe3O4-PEI-RGO nanohybrids exhibited high catalytic activity toward the degradation of dyes and pigments, which could be relevant to the high surface areas of Pd NPs and synergistic effect on transfer of electrons between reduced graphene oxide (RGO), PEI and Pd NPs. Notably, Pd NPs/Fe3O4-PEI-RGO nanohybrids were easily separated and recycled thirteen times without obvious decrease in system. Convincingly, Pd NPs/Fe3O4-PEI-RGO nanohybrids would be a promising catalyst for treating industrial wastewater.