Nanosheet of PdNiZn and nanosphere of PdNiZn/reduced‐graphene oxide (RGO) with sub‐3 nm spheres have been successfully synthesized through a facile oil‐water interfacial strategy. The morphology and composition of the films were determined by X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive analysis of X‐ray (EDAX) and elemental mapping. In the present study, we have developed a method to minimize the usage of precious Pd element. Due to the special structure and intermetallic synergies, the PdNiZn and PdNiZn/RGO nanoalloys exhibited enhanced catalytic activity and durability relative to Pd nanoparticles in Suzuki‐Miyaura C‐C cross‐coupling reaction. Compared to classical cross‐coupling reactions, this method has the advantages of a green solvent, short reaction times, low catalyst loading, high yields and reusability of the catalysts.