Sputtered W/B4C multilayers were determined by X-ray photoelectron spectroscopy, Raman scattering spectroscopy, scanning electron microscopy and atomic force microscopy synthetically. Two defect modes were observed in multilayers: buckle delamination and oxidation. This paper compares the chemical composition varies along multilayer depth and at different regions and tries to interpret the mechanism of defect evolution. The X-ray grazing incidence reflection profiles were compared to the theoretical value to estimate the influences from different defects. (C) 2015 Elsevier B.V. All rights reserved.