Optical absorption and photoluminescence emission properties of dehydroxylated MgO and CaO nanocrystals are discussed with respect to particle morphology and size. On MgO nanocubes with pronounced corner and edge features two emission bands at 3.4 and 3.3 eV result from the excitation of 4-coordinated surface O-4C(2-) anions in edges at 5.4 eV and of regular oxygen-terminated corners at 4.6 eV, respectively. Morphologically ill-defined CaO particles are a factor of 5 larger, do not display regular corner features, and show only one photoluminescence emission band at 3.0 eV. The associated excitation spectrum indicates electronic excitations above the energy required to excite regular oxygen- terminated CaO corners. It is concluded that in the case of morphologically well-defined MgO nanocubes variations in the next coordination of oxygen- terminated corners can effectively be probed by photoluminescence spectroscopy and thus allows for discrimination between 3-coordinated surface O2- in regular corner sites and kinks.