The effect Ме3+ (Al, Y, Sc, Fe, and Mn) cations on the structural properties and state of a zirconium dioxide surface layer is investigated. The thermal stability of the Ме3+ solid solutions based on a metastable zirconium dioxide modification is established via X-ray diffraction analysis. It is shown using X‑ray photoelectron spectroscopy that the distribution of surface–volume cationic modifier is determined by the type of cation. In Al-, Fe-, and Mn-ZrO2 systems, modifiers are mainly distributed over a surface; in Y and Sc-ZrО2, modifiers are distributed uniformly. The nature of the cation distribution affects the thermal stability of the solid solutions formed.