A 0.3 wt% Pt–0.3 wt% Re/Al 2 O 3 catalyst and monometallic 0.3 wt% Pt reference have been studied by X-ray absorption near-edge structure (XANES), hydrogen chemisorption, andn-heptane reforming, at stages during a series of oxychlorination/reduction cycles. The initial precalcined, chlorine-free system contains separate Pt 4+ and Re 7+ oxide clusters, which are reduced through a Re intermediate, yielding a Pt–Re alloy. Several chemical characteristics of the Re intermediate and the alloyed phase are revealed by the study. Subsequent oxychlorination of the reduced catalysts leads to the disruption of the alloy particles, producing initially Re 7+ oxide and Pt 4+ oxychloride species, with the latter eventually losing most of its chlorine ligands to form an oxide-like phase at higher treatment temperatures. The presence of chlorine influences the behavior of the subsequent reduction process, in particular, modifying the final properties of the zero-valent alloyed phase. The physical and chemical parameters affecting the Cl-induced changes are discussed on the basis of the XANES study.