A new X-ray diffraction technique is developed to probe structural variations at the interfaces between epitaxy thin films and single-crystal substrates. The technique utilizes three-wave Bragg-surface diffraction, where a symmetric Bragg reflection and an asymmetric surface reflection are involved. The propagation of the latter along the interfaces conveys structural information about the interfacial region between the substrate and epi-layers. The sample systems of Au/GaAs(001) are subject to the three-wave diffraction investigation using synchrotron radiation. The GaAs three-wave Bragg-surface diffractions, (006)/(1 (1) over bar3) and (006)/((1) over bar(1) over bar3), are employed. The images of the surface diffracted waves are recorded with an image plate. The obtained images show relative positions of diffraction spots near the image of the interfacial boundary, which give the variation of lattice constant along the surface normal and in-plane directions. With the aid of grazing-incidence diffraction, three-dimensional mapping of strain field at the interfaces is possible. Details about this diffraction technique and the analysis procedures are discussed. (c) 2006 Elsevier B.V. All rights reserved.