Site-specific functionalization of oxide nanostructures gives rise to novel optical and chemical surface properties. In addition, it can provide deeper insights into the electronic surface structure of the associated materials. We applied chemisorption of molecular hydrogen, induced by ultraviolet (UV) light, followed by vacuum annealing to MgO nanocubes to selectively decorate three-coordinated oxygen ions (oxygen corner sites, for simplicity) with protons. Fully dehydroxylated nanocubes exhibit 3.2 +/- 0.1 eV photoluminescence induced by 4.6 eV light, where both emission and absorption are associated with three-coordinated oxygen sites. We find that partially hydroxylated nanocubes show an additional photoluminescence feature at 2.9 0.1 eV. Interestingly, the excitation spectra of the 2.9 and 3.2 eV emission bands, associated with protonated and nonprotonated oxygen corner sites, respectively, nearly coincide and show well-pronounced maxima at 4.6 eV in spite of a significant difference in their local atomic and electronic structures. These observations are explained with the help of ab initio calculations, which reveal that (i) the absorption band at 4.6 eV involves four-coordinated O and Mg ions in the immediate vicinity of the corner sites and (ii) protonation of the three-coordinated oxygen ions eliminates the optical transitions associated with them and strongly red-shifts other optical transitions associated with neighboring atoms. These results demonstrate that the optical absorption bands assigned to topological surface defects are not simply determined by the ions of lowest coordination number but involve contributions due to the neighboring atoms of higher coordination. Thus, we suggest that the absorption band at 4.6 eV should not be regarded as merely a signature of the three-coordinated O2- ions but ought to be assigned to corners as multiatomic topological features. Our results also suggest that optical absorption signatures of protonated and nonprotonated sites of oxide surfaces can be remarkably similar.