We have studied the interfacial diffusion of Fe/Cr multilayers using synchrotron x-ray techniques, such as x-ray reflectivity, extended x-ray absorption fine structures (EXAFS), and high-resolution x-ray scattering. The results of x-ray reflectivity indicated that the interfacial roughness of Fe/Cr multilayers increased with the Cr-layer thickness. The Fourier transform (FT) of EXAFS data clearly showed that the Fe atoms dominantly diffused into the stable Cr layers at the Fe/Cr interface. The results of high-resolution x-ray scattering supported the interfacial diffusion of Fe atoms. Out study revealed that the dominantly interfacial diffusion of Fe atoms into the Cr layers effects the interfacial roughness of the Fe/Cr multilayers.