The ionization of xenon Rydberg atoms at metallic surfaces is examined. The data show that, when the effects of stray electric "patch" fields present on the surface are taken into account, ionization is well described by a simple over-the-barrier model. The patch fields are determined from direct measurements of the potential variations across the target surfaces using Kelvin probe force microscopy. Monte Carlo techniques are used to model the atom-surface interaction. The results confirm the important role that patch fields can play during Rydberg atom-surface interactions and suggest that such interactions can provide a sensitive probe of stray fields at surfaces. To demonstrate this, measurements of the threshold conditions required to observe ions resulting from surface ionization are used to estimate how large such stray fields can be. The data show that the stray fields can be sizable, as large as ∼ 10 3 V · cm -1 100 nm from the surface and ∼ 10 V · cm -1 500 nm from the surface, and illustrate the potential of Rydberg atoms for detecting and characterizing surface electric fields. Methods to enhance the surface ionization signal using electrode arrays patterned on a surface are investigated. Simulations show that bias voltages applied to a series of parallel wires comprised of two interleaved comb-shaped electrodes can have a dramatic impact on ion collection efficiency. It is suggested that such a surface can be used to efficiently collect low- n Rydberg atoms ( n [Special characters omitted.] 10). Significant progress towards fabrication of a functioning surface of 1 μm wide wires with 1 μm spacing is documented.