Synchrotron radiation techniques represent powerful tools to characterize materials down to the nanometer level. This paper presents a survey of the state-of-the-art synchrotron-based techniques which are particularly well-suited for investigating materials properties. Complementary X-ray absorption techniques such as extended X-ray absorption fine structure (EXAFS), X-ray magnetic circular dichroism (XMCD), photoemission electron microscopy (PEEM) are used to address the individual local atomic structure and magnetic moments in Fe–Cr model systems. The formation of atomic clusters/precipitates in such systems is also investigated by means of scanning transmission X-ray microscopy (STXM). Such advanced analytical techniques can not only offer valuable structural and magnetic information on such systems, they can also serve for validating computational calculations performed at different time and length scales which can help improve materials lifetime predictions.