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The effect of support on the performance of Pd₁Ag₁₀/Al₂O₃ and Pd₁Ag₁₀/CeO₂–ZrO₂ catalysts in the selective hydrogenation of diphenylacetylene (DPA) was studied. Characterization of the catalyst by DRIFTS-CO and HRTEM revealed the formation of a PdAg single-atom alloy (SAA) structure on the surface of PdAg nanoparticles, with Pd₁ sites isolated by Ag atoms. It was found that the use of CeO₂–ZrO₂ as a carrier makes it possible to increase the activity of the Pd₁Ag₁₀ catalyst by a factor of three without loss of selectivity compared to the reference Pd₁Ag₁₀/Al₂O₃. According to the HRTEM data, this catalytic behavior can be explained by an increase in the dispersion of Pd₁Ag₁₀/CeO₂–ZrO₂ compared to its Pd₁Ag₁₀/Al₂O₃ counterpart. As evidenced by DRIFTS-CO data, the high selectivity of the Pd₁Ag₁₀/CeO₂–ZrO₂ sample presumably stems from the stability of the structure of isolated Pd₁ sites on the surface of SAA Pd₁Ag₁₀/CeO₂–ZrO₂.