A direct correlation of structural properties with the spatial distribution of bound exciton luminescence in ZnO epitaxial layers has been achieved on a microscopic scale using highly spatially and spectrally resolved cathodoluminescence. The morphology of the high quality ZnO layer is characterized by a distinct domain structure. While the laterally integrated cathodoluminescence spectrum shows narrow (full width at half maximum <3meV) I8 luminescence, a pronounced emission line at I0∕I1 emerges in the local spectra taken at domain boundaries. In complete contrast, no I0∕I1 emission is found inside the domains. Monochromatic images further evidence the selective incorporation of impurities at the grain boundaries of domains. Micro mappings of the I8 peak wavelength directly visualize the strain relaxation across the domains toward their very center, where a drop in quantum efficiency indicates enhanced defect concentration.