The authors used a complement of depth-resolved cathodoluminescence spectroscopy (DRCLS), atomic force microscopy (AFM), and Kelvin probe force microscopy (KPFM) to correlate the formation of native point defects with interface chemical reactions as well as surface morphology. A wide array of ZnO crystals grown by both melt and hydrothermal growth methods display orders-of-magnitude variation in 2.1, 2.5, and 3.0 eV native point defect optical transitions at their free surface and as a function of depth on a nanometer scale. AFM surface morphology scans taken simultaneously with KPFM potential maps reveal large variations in surface morphology related to the growth method and subsequent processing. Notably, when DRCLS defect emissions are low, the surface roughness is low and the morphology matches its respective KPFM potential map. When DRCLS emissions vary with depth, the morphology and potential maps do not correlate. Indeed, the latter can vary by hundreds of meV across micron square areas. These subsurface electrical changes are consistent with DRCLS features and emphasize the contribution of surface morphology to electrically active interface defects. The relative strength of near band edge to deep level defect emissions exhibit a threshold dependence on surface roughness. (C) 2008 American Vacuum Society.