The application of microwave radiation (MWR) during materials synthesis can generate a wide range of interesting phenomena, such as rapid, low-temperature phase transitions and the formation of nonequilibrium phases. However, the underlying mechanisms by which MWR can influence processes like nucleation, crystallization, sintering, and grain growth remain unknown. A critical need for studying these mechanisms is the ability to quantitatively characterize the effects of MWR exposure on atomic structure. In this regard, synchrotron X-ray sources provide an opportunity to shed new light on electromagnetic (EM) field–assisted synthesis due to the availability of high-energy X-rays that enable a wide range of experimental characterization techniques. Here, we review the use of synchrotron X-ray sources for both ex situ and in situ studies of MWR-assisted synthesis. While many synchrotron-based tools are available to characterize the structural effects of MWR from the micron down to the atomic scale, work in this field is ongoing, and no clear consensus exists regarding the underlying mechanisms of EM field–mediated phase transitions. We discuss the instrumentation available to study field–matter interaction mechanisms and identify future needs in synchrotron characterization to better understand how EM fields can engineer advanced materials.