As an important surfactant, Pb surface alloying in surfactant-assisted epitaxy growth was studied by synchrotron radiation photoemission. As annealing causes the submonolayer Pb, distributed as two-dimensional islands on Cu(I 11), to form Pb-Cu surface alloy, Cu growth is also found to activate the Pb-Cu surface alloy formation on submonolayer Pb covered Cu(I 11). Whereas, different from the fact that the Pb-Cu surface alloy is replaced by a Pb over-layer when the Pb coverage increases up to 1.0 ML, Co deposition gives rise to the Pb-Co surface alloy even on the 1.0 ML Pb covered Cu(l 11) surface. In the Pb-Cu surface alloy the Pb 5d core level is shifted toward Fermi level by about 20 meV. Heating de-alloys the Pb-Co surface alloy, while the interface intermixture between Co film and Cu substrate is also enhanced at the same time. (c) 2005 Elsevier B.V. All rights reserved.