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The use of x-ray photoelectron spectroscopy allows measurements of the single-crystal nuclear and valence electron states of the rare-earth transition-metal Zintl phases Yb14MnSb11 and Yb14ZnSb11. The sample surfaces of Yb14MnSb11 and Yb14ZnSb11 were measured after reception, Ar+ ion bombardment, and in situ cutting, respectively.