This paper reports a facile, water-based and one-pot synthesis of tetrahedral Pd nanocrystals (Pd-TNPs) with high yield and good size monodispersity supported on reduced graphene oxide (RGO) nanosheets via a co-chemical reduction method. The key synthetic strategy employed a positively charged polyallylamine–Pd^II complex (PAH–Pd^II) with un-coordinated amine groups as a linker molecule to immobilize Pd^II species on the negatively charged graphene oxide (GO) surface through electrostatic interaction. As characterized by transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) techniques, well-defined Pd-TNPs with an average size of 9 nm were uniformly distributed on the RGO surface. The as-prepared Pd-TNPs/RGO nanohybrid with excellent colloidal stability in aqueous solution exhibits superior catalytic activity towards the degradation of methylene blue (MB) compared to both unsupported Pd-TNPs and Pd black. Thus, the resultant Pd-TNPs/RGO nanohybrid, as a promising heterogeneous catalyst, might have wide potential applications in water-based catalysis systems for the future.