The use of x-ray reflection interface microscopy (XRIM) to image molecular-scale topography at the aqueous–solid interface, in situ, is described. Specifically, we image interfacial topography of the orthoclase-(001)–aqueous solution interface at room temperature and describe the challenges associated with in situ XRIM imaging. The measurements show that the reflectivity signal for in situ XRIM measurements is substantially smaller than that for ex situ measurements, because of both intrinsic and extrinsic factors. There is also a systematic temporal reduction in the image intensity with increasing x-ray dose, revealing that interaction of the focused x-ray beam with the orthoclase interfaces leads to interfacial perturbations, presumably in the form of surface roughening. This image fading is localized to the x-ray beam footprint, suggesting that the primary damage mechanism is initiated by photoelectrons produced by x-ray beam absorption near the substrate–electrolyte interface. Finally, the role of aqueous solution composition in controlling the sensitivity of the orthoclase surface to x-ray beam-induced effects is explored. A substantial increase in the orthoclase (001) surface stability was observed in solutions having elevated ionic strength, apparently as a result of the reduced lifetime of radiation chemistry products at these conditions.