A simple and efficient solution-based method for the synthesis of Pd–Ni bimetallic nanoparticles (NPs) has been developed. A series of Pd–Ni bimetallic NPs were readily achieved by reduction of PdCl2 and Ni(acac)2 (acac = acetyl- acetonate) in the presence of oleylamine (OAm),oleic acid (OA) and benzyl alcohol. Furthermore, by using high-resolution transmission electron microscopy (HRTEM), energy-dispersive spectrometry (EDS) mapping and X-ray diffraction (XRD), we demonstrate that the as-prepared Pd–Ni bimetallic NPs have core–shell structures with a Pd-rich core and a Ni-rich shell. In addition, the as-obtained Pd–Ni bimetallic NPs with varying compositions show excellent catalytic activities in the Miyaura–Suzuki reaction. When the nickel molar percentage was 0.23 to 0.65, the conversion with the as-obtained Pd–Ni bimetallic catalysts was above 90%. It is believed that this strategy can be employed to produce a variety of other well-defined core–shell type multimetallic nano- structures.