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Auger electron spectroscopy (AES) as a method to characterize the ferroelectric polarization domains in magnesium-doped lithium niobate crystals is demonstrated. Preliminary measurements on a test sample show a clearly identifiable relative shift in the energy of the Auger oxygen KLL transition peak between poled (inverted) and un-poled domains. Auger electrons detected from the negative polarization domains (-Z) have a higher energy than those from the positive domains indicating a lower ionization energy at the -Z domain surface. The degree of electron energy separation between the −Z and +Z domains was found to be dependent on proximity to the domain boundary and was potentially diminished by the accumulated charge under the incident primary beam. Polarization domain resolution is demonstrated on both the micron and millimeter scale, suggesting potential applicability of this technique to surface investigation and domain structure characterization of nonlinear optical devices such as periodically poled lithium niobate.