Solid-state electrolytes can offer improved lithium-ion battery safety while potentially increasing the energy density by enabling alkali metal anodes. There have been significant research efforts to improve the ionic conductivity of solid-state electrolytes and the electrochemical performance of all-solid-state batteries; however, the root causes of their poor performance—interfacial reaction and subsequent impedance growth—are poorly understood. This is due to the dearth of effective characterization techniques for probing these buried interfaces. In situ and operando methodologies are currently under development for solid-state interfaces, and they offer the potential to describe the dynamic interfacial processes that serve as performance bottlenecks. This article highlights state-of-the-art solid–solid interface probing methodologies, describes practical limitations, and describes a future for dynamic interfacial characterization.