Dynamic structural changes and their kinetics of a Re(10)-cluster catalyst in the direct phenol synthesis from benzene and O(2) were investigated by in situ time-resolved Re L(III)-edge energy-dispersive XAFS (DXAFS). We have successfully monitored the structural transformation of active Re(10) clusters to inactive Re monomers in the course of the selective oxidation of benzene with O(2) on the catalyst by the DXAFS technique in a real time. The results obtained suggested that the Re(10) cluster transformed directly to the Re monomers, which showed first order kinetics with respect to the quantity of Re(10) clusters. The absence of undesirable intermediate structures with low phenol selectivity during the structural transformation may be an advantageous issue for the high phenol selectivity of 93.9% at 9.9% conversion in a pulse reaction and 87.7% at 5.8% conversion in a steady-state reaction on the Re(10)-cluster catalyst. The reactant benzene inhibited the unfavorable structural transformation of the Re(10) cluster to the Re monomers during the selective benzene oxidation to phenol.