The time-resolved reduction process of copper cations in/on ZSM-5 during temperature-programmed reduction (300-700 K) was studied by energy-dispersive X-ray absorption fine structure (DXAFS) as well as transmission electron microscopy (TEM). Two Cu-ZSM-5 samples with different Cu loadings were prepared by an ion-exchange method. The Cu K-edge DXAFS spectra for isolated Cu2+ species in the channels of ZSM-5 and CuO particles on the outer surfaces of ZSM-5 were recorded at an interval of 1 s during the reduction. The curve fitting analysis of the EXAFS data and the XANES analysis revealed that the isolated Cu2+ species in the channels were reduced stepwise. They were reduced to isolated Cu+ species at 400-450 K and the Cu+ species to Cu-0 metallic clusters at 550-650 K. Small clusters like Cu-4 were initially formed, followed by particle growth. A small part of them went out to the outer surfaces of ZSM-5 during the reduction. In contrast, CuO particles on the outer surfaces were reduced directly to Cu-0 metallic particles around 450 K.