Supported Au and Ni clusters as well as bimetallic AuNi clusters have been produced by laser vaporization of both pure bulk metals and alloy. Transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDS) experiments show that they have a narrow distribution size centered around 2.5 nm and that bimetallic clusters have the same composition as the vaporized Au0.5Ni0.5 alloy. X-ray photoemission spectroscopy (XPS) has been used to measure core level binding energy shifts of Au 4f(7/2) and Ni2p(3/2). The shifts observed in the bimetallic system show the combined effects of both alloying and surface local order in relation with strong Au surface segregation as deduced from previous low energy ion scattering (LEIS) experiments.