Mössbauer spectroscopy is a powerful experimental tool for the investigations on local electronic and vibrational properties of solids. On the other hand, the recently developing field of “spintronics”, where spins of conduction electrons play a key role for transport phenomena, is requiring to control the size and physical properties of materials in nanoscales. Using Mössbauer spectroscopy it becomes possible to investigate local magnetism and electron-spin polarization of materials, which can be important information for further development of spintronics. In this article, Mössbauer spectroscopic studies on spintronics-related materials in the early stage after the discovery of giant magnetoresistance effect are outlined briefly, and then recent studies on Heusler-alloy-based layered structures are introduced topically.