Energy-domain grazing-incidence (57)Fe-Mössbauer spectroscopy (E-GIMS) with synchrotron radiation (SR) has been developed to study surface and interface structures of thin films. Highly brilliant (57)Fe-Mössbauer radiation, filtered from SR by a (57)FeBO(3) single-crystal nuclear Bragg monochromator, allows conventional Mössbauer spectroscopy to be performed for dilute (57)Fe in a mirror-like film in any bunch-mode operation of SR. A theoretical and experimental study of the specular reflections from isotope-enriched ((57)Fe: 95%) and natural-abundance ((57)Fe: ∼2%) iron thin films has been carried out to clarify the basic features of the coherent interference between electronic and nuclear resonant scattering of (57)Fe-Mössbauer radiation in thin films. Moreover, a new surface- and interface-sensitive method has been developed by the combination of SR-based E-GIMS and the (57)Fe-probe layer technique, which enables us to probe interfacial complex magnetic structures in thin films with atomic-scale depth resolution.