From an interplay of atom-resolved noncontact atomic force microscopy, surface x-ray diffraction experiments, and density functional theory calculations, we reveal the detailed atomic-scale structure of the (100) surface of an insulating ternary metal oxide, MgAl2O4 (spinel). We surprisingly find that the MgAl2O4(100) surface is terminated by an Al and O-rich structure with a thermodynamically favored amount of Al atoms interchanged with Mg. This finding implies that so-called Mg-Al antisites, which are defects in the bulk of MgAl2O4, become a thermodynamically stable and integral part of the surface.