Using low-energy electron diffraction and angle-resolved photoemission spectroscopy, we investigated the lattice and electronic structures of the Pb(111) surface upon the adsorption of Au atoms at the low temperature T = 40 K. Unlike earlier results showing the formation of PbAu-alloy layers at room temperature, we found that Au atoms form a ultra-thin superstructure, Au/Pb(111)-3 × 3, on top of the Pb(111) surface. Moreover, three surface-state bands, S , S , and S , are induced within and immediately adjacent to the Pb bulk projected band gap centered at the surface zone boundary Formula: see text at the energies of - 0.02, - 1.05, and - 2.56 eV, respectively. First-principles calculation based on Au/Pb(111)-3 × 3 confirms the measured surface-state bands among which the most interesting are the S and S surface states. They are derived from surface resonances in Pb(111). Moreover, S , which disperses across Fermi level, exhibits a large anisotropic Rashba splitting with α of 1.0 and 3.54 eVÅ in the two symmetry directions centered at Formula: see text. The corresponding Rashba splitting of S band in Cu/Pb(111)-3 × 3 and Ag/Pb(111)-3 × 3 were calculated for comparison.