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In this paper low angle X-ray diffraction (XRD) and cross-sectional transmission electron microscopy (XTEM) studies of as-sputtered Ni-Si multilayers are reported. The modulation period, average composition and interfacial roughness determined from low-angle XRD combined with optical theory are compared with XTEM results. The relative importance of the effect of interface roughness on the modulated structure and the relation between the modulation period and the solid state amorphization reaction in the as-sputtered Ni-Si multilayers are discussed.