Metal redistribution and alloy formation in bimetallic model catalysts M–Au/HOPG (M = Pd, Ag, Cu) are studied using X-ray photoelectron spectroscopy with synchrotron radiation in a wide temperature range (25–500 °C) in ultrahigh vacuum. The composition, structure, and electronic properties of bimetallic particles are determined from the obtained spectral data at all stages of their formation. Thus, the work demonstrates the possibility of using photoelectron spectroscopy with synchrotron radiation to develop the methods of preparing supported bimetallic particles of various composition with controlled distribution of metals over their volumes.