Experiments in which a thermal-energy beam of xenon Rydberg atoms is directed at near grazing incidence onto a flat Au(111) surface are described that provide new insight into charge transfer and electron tunneling during atom/surface interactions. Analysis of the data shows that for the present range of principal quantum number n ; 13≤ n ≤20; ionization occurs at an atom/surface separation Z i = (4.5±0.9) n 2 a 0 ; where n 2 a 0 is the Bohr radius of the atom. This result is in good agreement with the value Z i ∼3.8 n 2 a 0 predicted by ab initio hydrogenic theory.