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Temperature programmed reduction (TPR) experiments were carried out over Pd/ZnO with different Pd loadings. Combined results with an X-ray diffraction method and X-ray photoelectron spectroscopy showed that a Pd–Zn alloy with a structure of PdZn was selectively produced in the course of TPR of Pd/ZnO. It was suggested that hydrogen retained in Pd spilled over to ZnO. The ZnO was reduced to metallic Zn, being converted to PdZn. The molar amounts of the ZnO reduced were practically the same as the those of Pd loaded. Hence, all the Pd loaded was completely transformed to the PdZn alloys upon reduction.